Method for producing high melting-point polyolefins

ABSTRACT

High-melting polyolefins can be prepared in bulk, in solution, in suspension or in the gas phase, the catalysts employed being metallocene compounds or π complex compounds of the formula                    
     in which 
     CpI and CpII represent carbanions having a cyclopentadienyl-containing structure, 
     πI and πII represent charged or electrically neutral π systems, 
     D represents a donor atom and 
     A represents an acceptor atom, 
     where D and A are linked by a reversible coordinate bond such that the donor groups assumes a positive (part) charge and the acceptor group assumes a negative (part) charge, 
     M represents a transition metal of sub-group III, IV, V or VI of the Periodic Table of the Elements (Mendeleev), including the lanthanides and the actinides, 
     X denotes one anion equivalent and 
     n denotes the number zero, one, two, three or four, depending on the charge of M.

FIELD OF THE INVENTION

The present invention relates to the use of π systems or of metallocenecompounds in which a transition metal with two o systems, and inparticular with aromatic π systems, such as anionic cyclopentadienylligands (carbanions) is complexed and the two systems are bondedreversibly to one another by at least one bridge of a donor and anacceptor, as organometallic catalysts in a process for the preparationof high-melting polyolefins by homo- or copolymerization of one or moremonomers from the group consisting of optionally substituted α-olefinshaving two or more C atoms. The coordinate bond formed between the donoratom and the acceptor atom produces a positive (part) charge in thedonor group and a negative (part) charge in the acceptor group:

BACKGROUND OF THE INVENTION

Metallocenes and their use as catalysts in the polymerization of olefinshave been known for a long time (EP-A 129 368 and the literature citedtherein). It is furthermore known from EP-A '368 that metallocenes incombination with aluminum-alkyl/water as cocatalysts are active systemsfor the polymerization of ethylene (thus, for example,methylaluminoxane=MAO is formed from 1 mol of trimethylaluminum and 1mol of water. Other stoichiometric ratios have also already been usedsuccessfully (WO 94/20506)). Metallocene in which the cyclopentadienylskeletons are linked to one another covalently via a bridge are alsoalready known. An example of the numerous patents and applications inthis field which may be mentioned is EP-A 704 461, in which the linkagegroup mentioned therein is a (substituted) methylene group or ethylenegroup, a silylene group, a substituted silylene group, a substitutedgermylene group or a substituted phosphine group. The bridgedmetallocenes are also envisaged as polymerization catalysts for olefinsin EP '461. In spite of the numerous patents and applications in thisfield, there continues to be a demand for improved catalysts which aredistinguished by a high activity, so that the amount of catalystremaining in the polymer can be set to a low level, and which aresuitable for the polymerization and copolymerization of olefins.

SUMMARY OF THE INVENTION

It has now been found that particularly advantageous catalysts can beprepared from bridged X complex compounds, and in particular frommetallocene compounds, in which the bridging of the two π systems isestablished by one, two or three reversible donor-acceptor bonds, inwhich in each case a coordinate or so-called dative bond which isoverlapped at least formally by an ionic bond forms between the donoratom and the acceptor atom, and in which one of the donor or acceptoratoms can be part of the particular associated π system. Thereversibility of the donor-acceptor bond also allows, in addition to thebridged state identified, by the arrow between D and A, the non-bridgedstate in which the two π systems can rotate against one another, forexample through an angle of 360°, as a result of their inherentrotational energy, without the integrity of the metal complex beingsurrendered. When the rotation is complete, the donor-acceptor bond“snaps in” again. If several donors and/or acceptors are present, such“snapping in” can already take place after angles of less than 360° havebeen passed through. π systems according to the invention which are tobe employed, for example metallocenes, can therefore be represented byjust a double arrow and the formula parts (Ia) and (Ib) or (XIIIa) and(XIIIb) to include both states.

DETAILED DESCRIPTION OF THE INVENTION

The invention accordingly relates to a process for the preparation ofhigh-melting polyolefins by homo- or copolymerization of one or moremonomers from the group consisting of optionally substituted α-olefinshaving 2 or more C atoms in the presence of organometallic catalystswhich can be activated by cocatalysts, which comprises employing as theorganometallic catalysts metallocene compounds of the formula

in which

CpI and CpII are two identical or different carbanions having acyclopentadienyl-containing structure, in which one to all the H atomscan be replaced by identical or different radicals from the groupconsisting of linear or branched C₁-C₂₀-alkyl, which can bemonosubstituted to completely substituted by halogen, mono- totrisubstituted by phenyl or mono- to trisubstituted by vinyl,C₆-C₁₂-aryl, halogenoaryl having 6 to 12 C atoms, organometallicsubstituents, such as silyl, trimethylsilyl or ferrocenyl, and 1 or 2can be replaced by D and A,

D denotes a donor atom, which can additionally carry substituents andhas at least one free electron pair in its particular bond state,

A denotes an acceptor atom, which can additionally carry substituentsand has an electron pair gap in its particular bond state,

where D and A are linked by a reversible coordinate bond such that thedonor group assumes a positive (part) charge and the acceptor groupassumes a negative (part) charge,

M represents a transition metal of sub-group III, IV, V or VI of thePeriodic Table of the Elements (Mendeleev), including the lanthanidesand actinides,

X denotes one anion equivalent and

n denotes the number zero, one, two, three or four, depending on thecharge of M,

or π complex compounds, and in particular metallocene compounds of theformula

 in which

πI and πII represent different charged or electrically neutral π systemswhich can be fused with one or two unsaturated or saturated five- orsix-membered rings,

D denotes a donor atom, which is a substituent of πI or part of the πsystem of πI and has at least one free electron pair in its particularbond state,

A denotes an acceptor atom, which is a substituent of πII or part of theπ system of πII and has an electron pair gap in its particular bondstate,

where D and A are linked by a reversible coordinate bond such that thedonor group assumes a positive (part) charge and the acceptor groupassumes a negative (part) charge, and where at least one of D and A ispart of the particular associated π system,

where D and A in their turn can carry substituents,

where each π system and each fused-on ring system can contain one ormore D or A or D and A and

wherein πl and πII in the non-fused or in the fused form, one to all theH atoms of the π system independently of one another can be substitutedby identical or different radicals from the group consisting of linearor branched C₁-C₂₀-alkyl, which can be monosubstituted to completelysubstituted by halogen, mono- to tri-substituted by phenyl or mono- totrisubstituted by vinyl, C₆-C₁₂-aryl, halogenoaryl having 6 to 12 Catoms, organometallic substituents, such as silyl, trimethylsilyl orferrocenyl, or one or two can be replaced by D and A, so that thereversible coordinate D→A bond (i) is formed between D and A, which areboth parts of the particular π system or the fused-on ring system, or(ii) of which D or A is part of the π system or of the fused-on ringsystem and in each case the other is substituent of the non-fused πsystem or the fused-on ring system,

M and X have the above meaning and

n denotes the number zero, one, two, three or four, depending on thecharges of M and those of π-I and π-II.

π systems according to the invention are substituted and unsubstitutedethylene, allyl, pentadienyl, benzyl, butadiene, benzene, thecyclopentadienyl anion and the species which result by replacement of atleast one C atom by a heteroatom.

Among the species mentioned, the cyclic species are preferred. Thenature of the coordination of such ligands (π systems) to the metal canbe of the s type or of the π type.

Such metallocene compounds of the formula (I) which are to be employedaccording to the invention can be prepared by reacting with one anothereither in each case a compound of the formulae (II) and (III)

or in each case a compound of the formulae (IV) and (V)

or in each case a compound of the formulae (VI) and (VII)

with elimination of M′X, in the presence of an aprotic solvent, or ineach case a compound of the formulae (VIII) and (III)

or in each case a compound of the formulae (IV) and (IX)

or in each case a compound of the formulae (X) and (VII)

with elimination of E(R¹R²R³)X and F(R⁴R⁵R⁶)X, in the absence or in thepresence of an aprotic solvent, in which

CpI, CpII, D, A, M, X and n have the above meaning,

CpIII and CpIV represent two identical or different non-chargedmolecular parts having a cyclopentadiene-containing structure, but areotherwise the same as CpI and CpII,

M′ denotes one cation equivalent of an alkali metal or alkaline earthmetal or Tl,

E and F independently of one another denote one of the elements Si, Geor Sn and

R¹, R², R³, R⁴, R⁵ and R⁶ independently of one another representstraight-chain or branched C₁-C₂₀-alkyl, C₆-C₁₂-aryl,C₁-C₆-alkyl-C₆-C₁₂-aryl, C₆-C₁₂-aryl-C₁-C₆-alkyl, vinyl, allyl orhalogen,

and where furthermore, in the formulae (VIII), (IX) and (X), hydrogencan replace E(R¹R²R³) and F(R⁴R⁵R⁶), and in this case X can alsorepresent an amide anion of the type R₂N⁻ or a carbanion of the typeR₃C⁻ or an alcoholate anion of the type RO^(θ), and where it isfurthermore possible to react compounds of the formulae (II) or (VIII)directly with a transition metal compound of the formula (VII) in thepresence of compounds of the formulae (V) or (IX).

In the reaction of (VIII) with (III) or (IV) with (IX) or (X) with(VII), in the case of the variant mentioned last, the structure (I)forms with elimination of amine R₂NH or R₂NE(R¹R²R³) or R₂NF(R⁴R⁵R⁶) ora hydrocarbon compound of the formula R₃CH or R₃CE(R¹R²R³) orR₃CF(R⁴R⁵R⁶) or an ether ROE(R¹R²R³) or ROF(R⁴R⁵R⁶), in which theorganic radicals R are identical or different and independently of oneanother are C₁-C₂₀-alkyl, C₆-C₁₂-aryl, substituted or unsubstitutedallyl, benzyl or hydrogen. Examples of the amine or hydrocarbon, ether,silane, stannane or germane eliminated are, for example, dimethylamine,diethylamine, di-(n-propyl)-amine, di-(isopropyl)-amine,di-(tert-butyl)-amine, tert-butylamine, cyclohexylamine, aniline,methyl-phenyl-amine, di-(allyl)-amine or methane, toluene,trimethylsilylamine, trimethylsilyl ether, tetramethylsilane and thelike.

It is also possible to react compounds of the formulae (II) or (VIII)directly with a transition metal compound of the formula (VII) in thepresence of compounds of the formulae (V) or (IX).

π complex compounds of the formula (XIII) in which the π systems arecyclic and aromatic (metallocenes) can be prepared analogously, thefollowing compounds being employed accordingly:

Open-chain π complex compounds are prepared by processes known to theexpert with incorporation of donor and acceptor groups.

According to the invention, for homo- or copolymerization of one or moreoptionally substituted α-olefins as monomers, the reaction is carriedout in the gas, solution, high pressure or slurry phase at −60 to +250°C., preferably 0 to 200° C., under 0.5 to 5000, preferably 1 to 3000bar, in the presence or absence of saturated or aromatic hydrocarbons orof saturated or aromatic halogeno-hydrocarbons and in the presence orabsence of hydrogen, the metallocene compounds or the π complexcompounds being employed as catalysts in an amount of 10¹ to 10¹² mol ofall the monomers per mole of metallocene or π complex compound, and itbeing furthermore possible to carry out the reaction in the presence ofLewis acids, Brönstedt acids or Pearson acids, or additionally in thepresence of Lewis bases.

Such Lewis acids are, for example, boranes or alanes, such asaluminum-alkyls, aluminum halides, aluminum alcoholates, organoboroncompounds, boron halides, boric acid esters or compounds of boron oraluminum which contain both halide and alkyl or aryl or alcoholatesubstituents, and mixtures thereof, or the triphenylmethyl cation.Aluminoxane or mixtures of aluminum-containing Lewis acids with waterare particularly preferred. According to current knowledge, all theacids act as ionizing agents which form a metallocenium cation, thecharge of which is compensated by a bulky, poorly coordinating anion.

According to the invention, the reaction products of such ionizingagents with metallocene compounds of the formula (I) can furthermore beemployed. They can be described by the formulae (XIa) to (XId)

in which

Anion represents the entire bulky, poorly coordinating anion and Baserepresents a Lewis base.

The catalysts of the formulae (I) and (XIII) which can be employedaccording to the invention can be present both in monomeric and indimeric or oligomeric form.

It is also possible to employ a plurality of D/A catalystssimultaneously, in order to establish a certain profile of theproperties of the material. Accordingly, it is also possible to employone or more D/A catalysts in combination with other metallocenes whichcontain no D/A bridge.

Examples of poorly coordinating anions are, for example,

B(C₆H₅)₄ ^(θ), B(C₆F₅)₄ ^(θ), B(CH₃)(C₆F₅)₃ ^(θ),

or sulfonates, such as tosylates or triflates, tetrafluoroborates,hexafluorophosphates or -antimonates, perchlorates, and voluminouscluster molecular anions of the carborane type, for example C₂B₉H₁₂ ^(θ)or CB₁₁H₁₂ ^(θ). If such anions are present, metallocene compounds canalso act as highly active polymerization catalysts in the absence ofaluminoxane. This is the case, above all, if one X ligand represents analkyl group, allyl or benzyl. However, it may also be advantageous toemploy such metallocene complexes with voluminous anions in combinationwith aluminum-alkyls, such as (CH₃)₃Al, (C₂H₅)₃Al, (n-/i-propyl)₃Al,(n-/t-butyl)₃Al, (i-butyl)₃Al, the isomeric pentyl-, hexyl- oroctylaluminum-alkyls or lithium-alkyls, such as methyl-Li, benzyl-Li orbutyl-Li, or the corresponding organo-Mg compounds, such as Grignardcompounds, or organo-Zn compounds. Such metal-alkyls on the one handtransfer alkyl groups to the central metal, and on the other handscavenge water or catalyst poisons from the reaction medium or monomerduring polymerization reactions. Metal-alkyls of the type described canalso advantageously be employed in combination with aluminoxanecocatalysts, for example in order to reduce the amount of aluminoxanerequired. Examples of boron compounds with which, when used, such anionsare introduced are:

triethylammonium tetraphenylborate,

tripropylammonium tetraphenylborate,

tri(n-butyl)ammonium tetraphenylborate,

tri(t-butyl)ammonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl(2,4,6-trimethylanilinium) tetraphenylborate,

trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,N,N-dimethyl(2,4,5-trimethylanilinium)tetrakis(pentafluorophenyl)borate,

trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate and

N,N-dimethyl(2,4,6-trimethylanilinium)tetrakis(2,3,4,6-tetrafluorophenyl)borate; dialkylammmonium salts, suchas:

di(i-propyl)ammonium tetrakis(pentafluorophenyl)borate and

dicyclohexylammonium tetrakis(pentafluorophenyl)borate;

tri-substituted phosphonium salts, such as:

triphenylphosphonium tetrakis(pentafluorophenyl)borate,

tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate and

tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate;

tritolylmethyl tetrakis(pentafluorophenyl)borate,

triphenylmethyl-tetraphenylborate (trityl-tetraphenylborate),

trityl tetrakis(pentafluorophenyl)borate,

silver tetrafluoroborate,

tris(pentafluorophenyl)borane and

tris(trifluoromethyl)borane.

The metallocene compounds to be employed according to the invention andthe π complex compounds can be employed in isolated form as the puresubstances for the (co)polymerization. However, it is also possible toproduce them and use them “in situ” in the (co)polymerization reactor ina manner known to the expert.

The first and the second carbanion CpI and CpII having acyclopentadienyl skeleton can be identical or different. Thecyclopentadienyl skeleton can be, for example, one from the groupconsisting of cyclopentadiene, substituted cyclopentadiene, indene,substituted indene, fluorene and substituted fluorene. 1 to 4substituents may be present per cyclopentadiene or fused-on benzenering. These substituents can be C₁-C₂₀-alkyl, such as methyl, ethyl,propyl, isopropyl, butyl or iso-butyl, hexyl, octyl, decyl, dodecyl,hexadecyl, octadecyl or eicosyl, C₁-C₂₀-alkoxy, such as methoxy, ethoxy,propoxy, isopropoxy, butoxy or iso-butoxy, hexoxy, octyloxy, decyloxy,dodecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, halogen, such asfluorine, chlorine or bromine, C₆-C₁₂-aryl, such as phenyl,C₁-C₄-alkylphenyl, such as tolyl, ethylphenyl, (i-)propylphenyl, (i-,tert-)butylphenyl or xylyl, halogenophenyl, such as fluoro-, chloro- orbromophenyl, naphthyl or biphenylyl, triorganyl-silyl, such astrimethylsilyl (TMS), ferrocenyl and D or A, as defined above. Fused-onaromatic rings can furthermore be partly or completely hydrogenated, sothat only the double bond of which both the fused-on ring and thecyclopentadiene ring have a portion remains. Benzene rings, such as inindene or fluorene, can furthermore contain one or two further fused-onbenzene rings. The cyclopentadiene or cyclopentadienyl ring and afused-on benzene ring can also furthermore together contain a furtherfused-on benzene ring.

In the form of their anions, such cyclopentadiene skeletons areexcellent ligands for transition metals, each cyclopentadienyl carbanionof the optionally substituted form mentioned compensating a positivecharge of the central metal in the complex. Individual examples of suchcarbanions are cyclopentadienyl, methylcyclopentadienyl,1,2-dimethyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, indenyl,phenylindenyl, 1,2-diethyl-cyclopentadienyl,tetramethyl-cyclopentadienyl, ethyl-cyclopentadienyl,n-butyl-cyclopentadienyl, n-octyl-cyclopentadienyl,β-phenylpropyl-cyclopentadienyl, tetrahydroindenyl,propyl-cyclopentadienyl, t-butylcyclopentadienyl,benzyl-cyclopentadienyl, diphenylmethyl-cyclopentadienyl,trimethylgermyl-cyclopentadienyl, trimethylstannyl-cyclopentadienyl,trifluoromethyl-cyclopentadienyl, trimethylsilyl-cyclopentadienyl,pentamethylcyclopentadienyl, fluorenyl, tetrahydro- andoctahydro-fluorenyl, fluorenyls and indenyls which are benzo-fused onthe six-membered ring, N,N-dimethylamino-cyclopentadienyl,dimethylphosphino-cyclopentadienyl, methoxy-cyclopentadienyl,dimethylboranyl-cyclopentadienyl and(N,N-dimethylaminomethyl)-cyclopentadienyl.

In addition to the first donor-acceptor bond between D and A which isobligatorily present, further donor-acceptor bonds can be formed ifadditional D and/or A are present as substituents of the particularcyclopentadiene systems or substituents or parts of the π systems. Alldonor-acceptor bonds are characterized by their reversibility describedabove. In the case of a plurality of D and A, these can occupy variouspositions of those mentioned. The invention accordingly relates both tothe bridged molecular states (Ia) and (XIIIa) and to the non-bridgedstates (Ib) and (XIIIb). The number of D groups can be identical to ordifferent from the number of A groups. Preferably, CpI and CpII arelinked via only one donor-acceptor bridge.

In addition to the D/A bridges according to the invention, covalentbridges can also be present. In these cases, the D/A bridges intensifythe stereorigidity and the heat stability of the catalyst. By changingbetween the closed and open D/A bond, sequence polymers are accessiblein the case of copolymers of different chemical composition.

The π complex compounds are likewise characterized by the presence of atleast one coordinate bond between donor atom(s) D and acceptor atom(s)A. Both D and A here can be substituents of their particular π systemsπI and πII or part of the π system, but always at least one of D and Ais part of the π system. π system here is understood as meaning theentire π system, which is optionally fused once or twice. The followingembodiments result from this:

D is part of the π system, A is a substituent of the π system;

D is a substituent of the π system, A is part of the π system;

D and A are part of their particular π system.

The following heterocyclic ring systems in which D or A is part of thering system may be mentioned as examples:

Important heterocyclic ring systems are the systems labeled (a), (b),(c), (d), (g), (m), (n) and (o); those labeled (a), (b), (c) and (m) areparticularly important.

In the case where one of D and A is a substituent of an associated ringsystem, the ring system is 3-, 4-, 5-, 6-, 7- or 8-membered with orwithout an electric charge, and can be further substituted and/or fusedin the manner described. 5- and 6-membered ring systems are preferred.The negatively charged cyclopentadienyl system is particularlypreferred.

The first and the second π system πI and πII respectively, if it isformed as a ring system, can correspond to CpI and CpII respectively inthe case where one of D and A is a substituent of the ring system.

Possible donor groups are, above all, those in which the donor atom D isan element of main group 5, 6 or 7, preferably 5 or 6, of the PeriodicTable of the Elements (Mendeleev) and has at least one free electronpair, and where the donor atom in the case of elements of main group 5is in a bond state with substituents, and in the case of elements ofmain group 6 can be in such a state; donor atoms of main group 7 carryno substituents. This is illustrated by the example of phosphorus P,oxygen O and chlorine Cl as donor atoms as follows, where “subst.”represents those substituents mentioned and “—Cp” represents the bond tothe cyclopentadienyl-containing carbanion, a line with an arrow has themeaning of a coordinate bond given in formula (I), and other linesdenote electron pairs present:

Possible acceptor groups are, above all, those in which the acceptoratom A is an element from main group 3 of the Periodic Table of theElements (Mendeleev), such as boron, aluminum, gallium, indium andthallium, is in a bond state with substituents and has an electron gap.

D and A are linked by a coordinate bond, where D assumes a positive(part) charge and A assumes a negative (part) charge.

A distinction is accordingly being made between the donor atom D and thedonor group and between the acceptor atom A and the acceptor group. Thecoordinate bond D→A is established between the donor atom D and acceptoratom A. The donor group denotes the unit consisting of the donor atom D,the substituent optionally present and the electron pairs present; theacceptor correspondingly denotes the unit of the acceptor atom A, thesubstituents and the electron gap present.

The bond between the donor atom or the acceptor atom and thecyclopentadienyl-containing carbanions can be interrupted by spacergroups in the manner of D—spacer—Cp or A—spacer—Cp. In the third of theabove formula examples, ═C(R)—represents such a spacer between O and Cp.Such spacer groups are, for example:

dimethylsilyl, diethysilyl, di-n-propylsilyl, diisopropylsilyl,di-n-butylsilyl, di-t-butylsilyl, d-n-hexylsilyl, methylphenylsilyl,ethylmethylsilyl, diphenylsilyl, di-(p-t-butylphenylsilyl),n-hexylmethylsilyl, cyclpentamethylsilyl, cyclotetramethylsilyl,cyclotrimethylenesilyl, dimethylgermanyl, diethylgermanyl, phenylamino,t-butylamino, methyl amino, t-butylphosphino, ethylphosphino,phenylphosphino, methylene, dimethylmethylene (i-propylidene),diethylmethylene, ethylene, dimethylethylene, diethylethylene,dipropylethylene, propylene, dimethylpropylene, diethylpropylene,1,1-dimethyl-3,3-dimethylpropylene, teramethyldisiloxane,1,1,4,4-tetramethylsilylethylene, diphenylmethylene.

D and A are preferably bonded to the cyclopentadienyl-containingcarbanion with-out a spacer.

D and A independently of one another can be on the cyclopentadiene (or-dienyl) ring or a fused-on benzene ring or on another substituent ofCpI and CpII respectively or πI and πII respectively. In the case of aplurality of D and A, these can occupy various positions of thosementioned.

Substituents on the donor atoms N, P, As, Sb, Bi, O, S, Se and Te and onthe acceptor atoms B, Al, Ga, In and Tl are, for example:C₁-C₁₂(cyclo)alkyl, such as methyl, ethyl, propyl, i-propyl,cyclopropyl, butyl, i-butyl, tert-butyl, cyclobutyl, pentyl, neopentyl,cyclopentyl, hexyl, cyclohexyl and the isomeric heptyls, octyls, nonyls,decyls, undecyls and dodecyls; the C₁-C₁₂-alkoxy groups which correspondto these; vinyl, butenyl and allyl; C₆-C₁₂-aryl, such as phenyl,naphthyl or biphenylyl and benzyl, which can be substituted by halogen,1 or 2 C₁-C₄-alkyl groups, C₁-C₄-alkoxy groups, nitro or halogenoalkylgroups, C₁-C₆-alkyl-carboxyl, C₁-C₆-alkyl-carbonyl or cyano (for exampleperfluorophenyl, m,m′-bis(trifluoromethyl)-phenyl and analogoussubstituents familiar to the expert); analogous aryloxy groups; indenyl;halogen, such as F, Cl, Br and I, 1-thienyl, disubstituted amino, suchas (C₁-C₁₂-alkyl)₂amino, and diphenylamino, tris-(C₁-C₁₂-alkyl)-silyl,NaSO₃-aryl, such as NaSO₃-phenyl and NaSO₃-tolyl, and C₆H₅—C≡C—;aliphatic and aromatic C₁-C₂₀-silyl, the alkyl substituents of which canadditionally be octyl, decyl, dodecyl, stearyl or eicosyl, in additionto those mentioned above, and the aryl substituents of which can bephenyl, tolyl, xylyl, naphthyl or biphenylyl; and those substitutedsilyl groups which are bonded to the donor atom or the acceptor atom via—CH₂—, for example (CH₃)₃SiCH₂—; and (C₁-C₁₂-alkyl)(phenyl)-amino,(C₁-C₁₂-alkylphenyl)₂amino, C₆-C₁₂-aryloxy with the abovementioned arylgroups, C₁-C₈-perfluoroalkyl and perfluorophenyl. Preferred substituentsare: C₁-C₆-alkyl, C₅-C₆-cycloalkyl, phenyl, tolyl, C₁-C₆-alkoxy,C₆-C₁₂-aryloxy, vinyl, allyl, benzyl, perfluorophenyl, F, Cl, Br,di-(C₁-C₆-alkyl)-amino and diphenylamino.

Donor groups are those in which the free electron pair is located on theN, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br and I; of these, N, P, O and Sare preferred. Examples of donor groups which may be mentioned are:(CH₃)₂N—, (C₃H₅)₂N—, (C₃H₇)₂N—, (C₄H₉)₂N—, (C₆H₅)₂N—, (CH₃)₂P—,(C₂H₅)₂P—, (C₃H₇)₂P—, (i—C₃H₇)₂P—, (C₄H₉)₂P—, (t—C₄H₉)₂P—,(cyclohexyl)₂P—, (C₆H₅)₂P—, CH₃O—, CH₃S—, C₆H₅S—, —C(C₆H₅)═O, —C(CH₃)═O,—OSi(CH₃)₃ and —OSi(CH₃)₂-t-butyl, in which N and P each carry a freeelectron pair and O and S each carry two free electron pairs, and wherein the last two examples mentioned, the double-bonded oxygen is bondedvia a spacer group, and systems such as the pyrrolidone ring, where thering members other than N also act as spacers.

Acceptor groups are those in which an electron pair gap is present on B,Al, Ga, In or Tl, preferably B or Al; examples which may be mentionedare (CH₃)₂B—, (C₂H₅)₂B—, H₂B—, (C₆H₅)₂B—, (CH₃)(C₆H₅)B—, (vinyl)₂B—,(benzyl)₂B—, Cl₂B—, (CH₃O)₂B—, Cl₂Al—, (CH₃)Al—, (i—C₄H₉)₂Al—,(Cl)(C₂H₅)₂Al—, (CH₃)₂Ga—, (C₃H₇)₂Ga—, ((CH₃)₃Si—CH₂)₂Ga—, (vinyl)₂Ga—,(C₆H₅)₂Ga—, (CH₃)₂In—, ((CH₃)₃Si—CH₂)₂In—, (cyclopentadienyl)₂In—.

Those donor and acceptor groups which contain chiral centers or in which2 substituents form a ring with the D or A atom are furthermorepossible. Examples of these are, for example,

Preferred donor-acceptor bridges between CpI and CpII are, for example,the following:

One or both π systems πI and/or πII can be present as a heterocyclicring in the form of the above ring systems (a) to (r). D here ispreferably an element of main group 5 or 6 of the Periodic Table of theElements (Mendeleev); A here is preferably boron. Some examples of suchhetero-π systems, in particular heterocyclic compounds, are:

R and R′=H, alkyl, aryl or aralkyl, for example methyl, ethyl, t-butyl,phenyl or o,o′-(di-i-propyl)-phenyl.

Examples of heterocyclic radicals are: pyrrolyl, methylpyrrolyl,dimethylpyrrolyl, trimethylpyrrolyl, tetramethylpyrrolyl,t-butylpyrrolyl, di-t-butylpyrrolyl, indolyl, methylindolyl,dimethylindolyl, t-butylindolyl, di-t-butylindolyl,tetramethylphospholyl, tetraphenylphospholyl, triphenylphospholyl,trimethylphospholyl, phosphaindenyl, dibenzophospholyl(phosphafluorenyl) and dibenzopyrrolyl.

Preferred donor-acceptor bridges between πI and πII are, for example,the following: N→B, N→Al, P→B, P→Al, O→B, O→Al, Cl→B, Cl→Al, C═O→B andC═O→Al, where both atoms of these donor-acceptor bridges can be part ofa hetero-π system or one atom (donor or acceptor) is part of a π systemand the other is a substituent of the second π system, or where bothatoms are substituents of their particular ring and one of the ringsadditionally contains a heteroatom.

According to the above depiction, the two ligand systems πI and πII canbe linked by one, two or three donor-acceptor bridges. This is possiblesince, according to the invention, formula (Ia) contains the D→A bridgedescribed, but the ligand systems πI and πII can carry further D and Aas substituents or hetero-π centers; the number of resulting additionalD→A bridges is zero, one or two. The number of D and A substituents onπI and πII respectively can be identical or different. The two ligandsystems πI and πII can additionally be bridged covalently. (Examples ofcovalent bridges are described above as spacer groups.) However,compounds without a covalent bridge, in which πI and πII accordingly arelinked only via a donor-acceptor bridge, are preferred.

M represents a transition metal from sub-group 3, 4, 5 or 6 of thePeriodic Table of the Elements (Mendeleev), including the lanthanidesand actinides; examples which may be mentioned are: Sc, Y, La, Sm, Nd,Lu, Ti, Zr, Hf, Th, V, Nb, Ta and Cr. Ti, Zr and Hf are preferred.

In the formation of the metallocene structure or π complex structure, ineach case a positive charge of the transition metal M is compensated byin each case a cyclopentadienyl-containing carbanion. Positive chargeswhich still remain on the central atom M are satisfied by further,usually monovalent anions X, two identical or different anions of whichcan also be linked to one another (dianions,

for example monovalently or divalently negative radicals from identicalor different, linear or branched, saturated or unsaturated hydrocarbons,amines, phosphines, thioalcohols, alcohols or phenols. Simple anionssuch as Cr₃ ⁻, NR₂ ⁻, PR₂ ⁻, OR⁻, SR⁻ and the like can be bonded bysaturated or unsaturated hydrocarbon or silane bridges, dianions beingformed and it being possible for the number of bridge atoms to be 0, 1,2, 3, 4, 5 or 6, 0 to 4 bridge atoms being preferred and 1 or 2 bridgeatoms particularly preferred. The bridge atoms can also carry furtherhydrocarbon substituents R in addition to H atoms. Examples of bridgesbetween the simple anions are, for example, 13 CH₂—, —CH₂—CH₂—,—(CH₂)₃—, CH═CH, —(CH═CH)₂—, —CH═CH—CH₂—, CH₂—CH═CH—CH₂—, —Si(CH₃)₂— andC(CH₃)₂—. Examples of X are: hydride, chloride, methyl, ethyl, phenyl,fluoride, bromide, iodide, the n-propyl radical, the i-propyl radical,the n-butyl radical, the amyl radical, the i-amyl radical, the hexylradical, the i-butyl radical, the heptyl radical, the octyl radical, thenonyl radical, the decyl radical, the cetyl radical, methoxy, ethoxy,propoxy, butoxy, phenoxy, dimethylamino, diethylamino, methylethylamine,di-t-butylamino, diphenylamino, diphenylphosphino,dicyclohexylphosphino, dimethylphosphino, methylidene, ethylidene,propylidene and the ethylene glycol dianion. Examples of dianions are1,4-diphenyl-1,3-butadienediyl, 3-methyl-1,3-pentadienediyl,1,4-dibenzyl-1,3-butadienediyl, 2,4-hexadienediyl, 1,3-pentadienediyl,1,4-ditolyl-1,3 -butadienediyl, 1,4-bis(trimethylsilyl-1,3-butadienediyland 1,3-butadienediyl. 1,4-Diphenyl-1,3-butadienediyl,1,3-pentadienediyl, 1,4-dibenzyl-1,3-butadienediyl, 2,4-hexanedienediyl,3-methyl-1,3-pentadienediyl, 1,4-ditolyl-1,3-butadienediyl and1,4-bis(trimethylsilyl)-1,3-butadienediyl are particularly preferred.Further examples of dianions are those with heteroatoms, for example ofthe structure

where the bridge has the meaning given. Weakly or non-coordinatinganions of the abovementioned type are, moreover, particularly preferredfor charge compensation.

The activation by such voluminous anions is effected, for example, byreaction of the D/A-π complex compounds, in particular theD/A-metallocenes, with tris-(pentafluorophenyl)-borane, triphenylborane,triphenylaluminum, trityl tetrakis-(pentafluorophenyl)-borate orN,N-dialkylphenylammonium tetrakis-(pentafluorophenyl)-borate or thecorresponding phosphonium or sulfonium salts of borates, or alkali metalor alkaline earth metal, thallium or silver salts of borates,carboranes, tosylates, triflates, perfluorocarboxylates, such astrifluoroacetate, or the corresponding acids. D/A-metallocenes in whichthe anion equivalent X represents alkyl, allyl, aryl or benzyl groupsare preferably employed here. Such derivatives can also be prepared “insitu” by reacting D/A metallocenes with other anion equivalents, such asX=F, Cl, Br, OR and the like, beforehand with aluminum-alkyls,organolithium compounds or Grignard compounds or zinc- or lead-alkyls.The reaction products obtainable therefrom can be activated withabovementioned boranes or borates without prior isolation.

The index n assumes the value zero, one, two, three or four, preferablyzero, one or two, depending on the charge of M. The abovementionedsub-group metals can in fact assume valencies/charges of two to six,preferably two to four, depending inter alia on which of the sub-groupsthey belong to, in each case two of these valencies/charges beingcompensated by the carbanions of the metallocene compound. In the caseof La³⁺, the index n accordingly assumes the value one, and in the caseof Zr⁴⁺ it assumes the value two; in the case of Sm²⁺, n is zero.

To prepare the metallocene compounds of the formula (I), either in eachcase a compound of the above formulae (II) and (III) or in each case acompound of the above formulae (IV) and (V) or in each case a compoundof the above formulae (VI) and (VII) or in each case a compound of theabove formulae (VIII) and (III) or in each case a compound of the aboveformulae (IV) and (IX) or in each case a compound of the above formulae(X) and (VII) are reacted with one another, with elimination orsplitting off of alkali metal-X, alkaline earth metal-X₂, silyl-X,germyl-X, stannyl-X or HX compounds, in an aprotic solvent attemperatures from −78° C. to +120° C., preferably from −40° C. to +70°C., and in a molar ratio of (II):(III) or (IV):(V) or (VI):(VII) or(VIII):(III) or (IV):(IX) or (X):(VII) of 1:0.5-2, preferably 1:0.8-1.2,particularly preferably 1:1. In the cases of reaction of (VIII) with(III) or (IV) with (IX) or (X) with (VII), it is possible to dispensewith an aprotic solvent if (VIII), (IX) or (X) is liquid under thereaction conditions. Examples of such compounds eliminated or split offare: TlCl, LiCl, LiBr, LiF, LiI, NaCl, NaBr, KCl, KF, MgCl₂, MgBr₂,CaCl₂, CaF₂, trimethylchlorosilane, triethylchlorosilane,tri-(n-butyl)-chlorosilane, triphenylchlorosilane,trimethylchlorogermane, trimethylchlorostannane, dimethylamine,diethylamine, dibutylamine and other compounds which can be ascertainedby the expert from the abovementioned substitution pattern.

Compounds of the formula (II) and (IV) are thus carbanions having acyclopentadienyl skeleton or a heterocyclic skeleton which contain 1 to3 donor groups, covalently bonded or incorporated as heterocyclic ringmembers and are used for the D/A bridge formation, and have a cation asa counter-ion to the negative charge of the cyclopentadienyl skeleton.Compounds of the formula (VIII) are non-charged cyclic skeletons withlikewise 1 to 3 donor groups used for D/A bridge formation, but withleaving groups E(R¹R²R³) which can easily be split off, such as silyl,germyl or stannyl groups or hydrogen, instead of the ionic groups.

The second component for formation of the metallocene compounds to beemployed according to the invention, that is to say the compound of theformula (III) or (V), is likewise a carbanion having a cyclopentadienylskeleton which is identical to the cyclopentadienyl skeleton of thecompound (II) or (IV) or different from this, but carries 1 to 3acceptor groups instead of the donor groups. In a corresponding manner,compounds of the formula (IX) are uncharged cyclopentadiene skeletonshaving 1 to 3 acceptor groups and likewise leaving groups F(R⁴R⁵R⁶)which can easily be split off.

In a completely analogous manner, compounds of the formulae (VI) or (X)are starting substances with a preformed D→A bond which arecarbanion-countercation compounds or uncharged cyclopentadienestructures with a possible 1 to 3 D→A bonds in total and give themetallocene compounds (I) by reaction with compounds of the formula(VII).

The two starting substances of the preparation process, that is to say(II) and (III) or (IV) and (V) or (VI) and (VII) or (VIII) and (III) or(IV) and (IX) or (X) and (VII) react spontaneously when broughttogether, with simultaneous formation of the donor-acceptor group —D→A—or complexing of the metal cation M with elimination of M′X orE(R¹R²R³)X or F(R⁴R⁵R⁶)X or HX. In the description of the donor-acceptorgroup, the substituents on D and A have been omitted for clarity.

M′ is one cation equivalent of an alkali metal or alkaline earth metal,such as Li, Na, K, ½Mg, ½Ca, ½Sr, ½Ba or thallium.

The compounds of the formula (XIIIa+b) are prepared analogously in theabove-mentioned manner.

Solvents for the preparation process are aprotic, polar or non-polarsolvents, such as aliphatic and aromatic hydrocarbons or aliphatic andaromatic halogeno-hydrocarbons. Other aprotic solvents such as are knownto the expert are also possible in principle, but because of the easierworking up, those with boiling points which are too high are lesspreferred. Typical examples are: n-hexane. cyclohexane, pentane,heptane, petroleum ether, toluene, benzene, chlorobenzene, methylenechloride, diethyl ether, tetrahydrofuran and ethylene glycol dimethylether.

The starting substances of the formulae (II), (III), (IV) and (V) can beprepared by processes known from the literature or analogously to these.Thus, for example, trimethylsilyl-cyclopentadiene, which is available onthe market, can be reacted first with butyl-lithium and then withtrimethylsilyl chloride to give bis(trimethylsilyl)-cyclopentadieneanalogously to J. of Organometallic Chem. (1971), 29, 227. This productcan in turn be reacted with boron trichloride to givetrimethylsilyl-cyclopentadienyl-dichloroborane (analogously to J. ofOrganometallic Chem. (1979), 169, 327), which finally can be reactedwith titanium tetrachloride analogously to J. of Organometallic Chem.(1979), 169, 373 to give dichloroboryl-cyclopentadienyl-titaniumtrichloride. This compound mentioned last is already a prototype of thecompounds of the formula (III); the compound mentioned last canfurthermore be reacted selectively with trimethylaluminum, the twochlorine atoms bonded to the boron atom being replaced by methyl groups,a further compound of the formula (III) being demonstrated.Cyclopentadienyl-thallium, which is available on the market, can bereacted with chloro-diphenylphosphine and further with butyl-lithiumanalogously to the process description in J. Am. Chem. Soc. (1983) 105,3882 and Organometallics (1982) 1, 1591, a prototype of compounds of theformula (II) being obtained. The formation ofdimethylstannyl-diphenylphosphine-indene by reaction of indene firstwith butyl-lithium, as already mentioned above, and then withchlorodiphenylphosphine may be mentioned as a further example; furtherreaction, first again with butyl-lithium and then withchloro-tributyltin, gives the compound mentioned, which, after furtherreaction with zirconium tetrachloride, givesdiphenylphosphino-indenyl-zirconium trichloride as a representative ofcompounds of the formula (IV). Such syntheses and preparation proceduresare familiar to the expert operating in the field of organometallic andorganoelemental chemistry and are published in numerous literaturereferences, of which only a few are given by way of example above.

The examples described below show how such heterocyclic precursors andcatalysts according to the invention are accessible. Thus,pyrrolyl-lithium (formula II) can be prepared from pyrrole by reactionwith butyl-lithium, as described, for example, in J. Amer. Chem. Soc.(1982), 104, 2031. Trimethylstannyl-phosphol (formula VIII) is obtainedby reaction of 1-phenylphosphol with lithium, followed by aluminumtrichloride, phospholyl-lithium (formula II) being formed, which in turnfurther reacts with trimethylchlorostannane to givetrimethylstannyl-phosphol. Cf.: J. Chem. Soc. Chem. Comm. (1988), 770.This compound can be reacted with titanium tetrachloride to givephospholyl-titanium trichloride (formula IV).

The metallocene compounds to be employed according to the invention areout-standingly suitable as catalysts in processes for the homo- andcopolymerization of one or more optionally substituted α-olefins in thegas, solution, high pressure or slurry phase at −60 to +250° C.,preferably 0 to 200° C., under a pressure of 0.5 to 5000 bar, preferably1 to 3000 bar, it being possible to carry out the reaction in thepresence or absence of saturated or aromatic hydrocarbons or ofsaturated or aromatic halogeno-hydrocarbons. Such polymerizations can becarried out discontinuously or, preferably, continuously. They can alsobe carried out by the semibatch process. Such processes can also becarried out in more than one reactor or reaction zone. In the case of aplurality of reaction zones, the polymerization can be carried out underdifferent polymerization conditions. Thus, a prepolymer which isparticularly suitable as a heterogeneous catalyst for the actual(co)polymerization in further reactors can be formed in one reactor.Heterogeneous D/A catalysts on inorganic supports are particularlysuitable for the formation of such prepolymers. 10¹ to 10¹² mol of(co)monomers are reacted per mole of π complex compounds or metallocenecompounds. The π complex compounds or metallocene compounds can beemployed together with cocatalysts. The ratio of the amounts between theπ complex compounds or metallocene compound and cocatalyst is 1 to100,000 mol of cocatalyst per mole of π complex compound or metallocene.Cocatalysts are understood as meaning, for example, aluminoxanecompounds such as those of the formula

in which

R represents C₁-C₂₀-alkyl, C₆-C₁₂-aryl or benzyl and

n denotes a number from 2 to 50, preferably 10 to 35.

It is also possible to employ a mixture of various aluminoxanes or amixture of precursors thereof (aluminum-alkyls) in combination withwater (in gaseous, liquid, solid or bonded form, for example as water ofcrystallization). The water can also be fed in as (residual) moisture ofthe polymerization medium, of the monomer or of a support, such assilica gel.

The bonds projecting from the square brackets of formula (XI) contain Rgroups or AlR₂ groups as end groups of the oligomeric aluminoxane. Suchaluminoxanes are as a rule present as a mixture of a plurality of themof different chain lengths. Fine analysis has also shown aluminoxaneswith a cyclic or cage-like structure. Aluminoxanes are compounds whichare available on the market. In the specific case of R═CH₃,methylaluminoxanes (MAO) are referred to.

Further cocatalysts are aluminum-alkyls, lithium-alkyls or organo-Mgcompounds, such as Grignard compounds, or partly hydrolyzed organoboroncompounds. Preferred cocatalysts are aluminoxanes.

The activation with the cocatalysts or the production of the voluminousnon- or weakly coordinating anions can be carried out in an autoclave orin a separate reaction vessel (preforming). The activation can becarried out in the presence or absence of the monomer(s) to bepolymerized. The activation can be carried out in an aliphatic oraromatic or halogenated solvent or suspending agent.

The π complex compounds or the metallocene compounds and thealuminoxanes can be employed both as such in homogeneous form andindividually or together in heterogeneous form on supports. The supportmaterial here can be inorganic or organic in nature, such as silica gel,Al₂O₃, MgCl₂, NaCl, cellulose derivatives, starch and polymers, such aspolyethylene or polypropylene. It is equally possible here to apply theπ complex compound or the metallocene compound first or to apply thealuminoxane first, to the support, and then to add the other particularcomponent. Equally, however, the it complex compound or the metallocenecompound can also be activated in homogeneous or heterogeneous form withthe aluminoxane and the activated metallocene compound can then beapplied to the optionally aluminoxane-charged support.

Support materials are preferably treated by heat and/or chemicals inorder to adjust the water content or the OH group concentration to adefined value or to keep it as low as possible. A chemical pretreatmentcan comprise, for example, reaction of the support with aluminum-alkyl.Inorganic supports are usually heated at 100° C. to 1000° C. for 1 to100 hours before use. The surface area of such inorganic supports, inparticular of silica (SiO₂), is between 10 and 1000 m²/g, preferablybetween 100 and 800 m²/g. The particle diameter is between 0.1 and 500micrometers (μ), preferably between 10 and 200 μ.

Olefins which are to be reacted by homo- or copolymerization are, forexample, ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene,oct-1-ene, 3-methyl-but-1-ene, 4-methyl-pent-1-ene, 4-methyl-hex-1-eneand iso-octene.

Such olefins can furthermore be substituted, for example by phenyl,substituted phenyl, halogen, the esterified carboxyl group or the acidanhydride group; compounds of this type are, for example, styrene,methylstyrene, chlorostyrene, fluorostyrene, 4-vinyl-biphenyl,vinyl-fluorene, vinyl-anthracene, methyl methacrylate, ethyl acrylate,vinylsilane, trimethyl-allylsilane, vinyl chloride, vinylidene chloride,tetrafluoroethylene, vinylcarbazole, vinylpyrrolidone, vinyl ethers andvinyl esters. Ring-opening polyadditions, for example of lactones, suchas ε-caprolactone or δ-valerolactone, or of lactarns, such asε-caprolactam, are furthermore possible according to the invention.Preferred monomers are: ethylene, propylene, butene, hexene, octene andmethyl methacrylate.

The homo- or copolymerizations or polyadditions to be carried out usingthe π complex compounds or metallocene compounds according to theinvention are carried out adiabatically or isothermally. These are highpressure processes in autoclaves or tube reactors, solution processesand also polymerization in bulk, processes in the slurry phase instirred reactors or loop reactors, and processes in the gas phase, thepressures for the slurry, solution and gas phase not exceeding 65 bar.All these processes have been known for a long time and are familiar tothe expert. It is an advantage of the π complex compounds andmetallocene compounds according to the invention that, by choice of thesubstituents, they can be prepared both as soluble π complex compoundsor metallocene compounds optionally applied to supports and as insolubleπ complex compounds or metallocene compounds. Soluble π complexcompounds and metallocene compounds are employed for the high pressureprocess and the solution process; heterogeneous metallocene compoundsare employed in the slurry phase and the gas phase.

(Co)polymers which can be prepared according to the invention aredistinguished by a high crystallinity and optimized melting range. Thisis achieved by a low degree of branching in the case of polyethylene andby a high tacticity (isotactic or syndiotactic) in the case of polymersof olefins having 3 or more C atoms. Copolymers are distinguished by ahigh regularity in the incorporation of the comonomers. Examples of suchpolymers are high-density linear polyethylene (HDPE), isotacticpolypropylene (iPP), syndiotactic polypropylene (sPP), i- ors-polybutene or -polyhexene, polyoctene, linear low-density copolymers,for example ethylene with C₃-C₈-α-olefin (linear low densitypolyethylene LLDPE), that is to say ethylene/propylene,ethylene/butylene, ethylene/hexene and ethylene/octene and furthermore,for example, propylene/butylene, propylene/hexene and others. HDPE,LLDPE with butylene, hexene or octene as comonomers, iPP and sPP arepreferred.

The π complex compounds to be employed according to the invention, inparticular the metallocene compounds, allow a defined opening of the twocyclopentadienyl skeletons like a beak due to the donor-acceptor bridge,a controlled selectivity, a controlled molecular weight distribution anda uniform incorporation of (co)monomers being ensured, in addition to ahigh activity. As a result of a defined beak-like opening, there is alsospace for voluminous (co)monomers. A high uniformity in the molecularweight distribution furthermore results from the uniform and definedsite of the polymerization taking place by insertion (single sitecatalyst).

The molecular weight distribution can be modified (broadened) in acontrolled manner by employing a plurality of D/A catalystssimultaneously, in order to establish a certain profile of properties ofthe material. Accordingly, it is also possible to employ one or more D/Acatalysts in combination with other metallocenes which have no D/Abridge.

The D/A structure can have the effect of extra-stabilizing the catalystsup to high temperatures, so that the catalysts can also be employed inthe high temperature range. The possible thermal dissociation of thedonor-acceptor bond is reversible and, as a result of thisself-organization process and self-repair mechanism, leads toparticularly high-quality catalyst properties. The D/A metallocenestructures according to the invention allow, for example, a degree ofdefect-free polyethylene formation which cannot be achieved withconventional catalysts. Correspondingly, the ethene polymers can haveexceptionally high melting points, for example above 135° C. to 160° C.(maximum of the DSC curve). Linear polyethylenes which are obtaineddirectly in the polymerization process preferably include those whichhave melting points of 140 to 160° C. (maxima of the DSC curves),preferably 142 to 160° C., particularly preferably 144 to 160° C.,especially preferably 146 to 160° C. This applies in particular to thosewhich can be prepared with the metallocene compounds claimed. Comparedwith the known polyethylenes, such novel high-melting polyethylenesshow, for example, improved mechanical properties and heat distortionperformance (sterilizability for medical applications) and as a resultopen up possibilities of use which did not hitherto seem possible forpolyethylene and, for example, would hitherto be met only by highlytactic polypropylene. Further features are high melting enthalpies andhigh PE molecular weights.

Within a wide temperature range, the PE molecular weight is reduced byincreasing the polymerization temperature without a noticeable reductionin activity and without leaving overall the range of industriallyadvantageous high PE molecular weights and high PE melting points.

For the preparation of isotactic polyolefins, for example,quasi-rac-bis(indenyl)metallocenes with a D/A bridge, which canadditionally carry, for example, alkyl, aryl and/or silyl substituentsor benzo-fused structures, for example in position 2 or in position 4,5, 6 or 7, to increase the molecular weight and isotacticity and meltingpoint, are particularly suitable. However,D/A-bis(cyclopentadienyl)-metallocenes with (3,3′) substitution patternsof comparable symmetry are also possible.

D/A-bridged (cyclopentadienyl)(fluorenyl)-metallocenes or(cyclopentadienyl)(3,4-disubstituted cyclopentadienyl)-metallocenes arecorrespondingly suitable, for example, for the preparation ofsyndiotactic polyolefins.

It has furthermore been found that metallocene compounds and π complexcompounds of suitable symmetry which are to be employed according to theinvention have the effect of a stereospecific (isotactic, syndiotactic)polymerization on α-olefins from 3 C atoms, but induce an increasinglynon-specific (atactic) linkage of the monomer units on the same monomerin the upper part of the temperature range mentioned. This phenomenonhas not yet been investigated completely, but could coincide with theobservation that coordinate bonds which are overlapped by an ionic bond,such as the donor-acceptor bonds in the metallocene compounds accordingto the invention, show an increasing reversibility at a highertemperature. It has furthermore been found, for example in the case ofethylene-propylene copolymerization, that if the same amount of the twocomonomers is available, a highly propylene-containing copolymer isformed at a low copolymerization temperature, while as thepolymerization temperature increases, the propylene content decreases,until finally predominantly ethylene-containing polymers (LLDPE) areformed at a high temperature. The reversible dissociation andassociation of the D/A structure and the rotation of the π skeletonsagainst one another which becomes possible as a result can be shownschematically as follows:

Another valuable property of the D/A-π complex compounds, for exampleD/A-metallocene compounds, according to the invention is the possibilityof self-activation and therefore of dispensing with expensive catalysts,in particular in the case of dianionic

derivatives.

In this case, the acceptor atom A bonds an X ligand in the open form ofthe D/A-π complex compounds, for example D/A-metallocene compound, forexample one side of a dianion, to form a zwitterionic metallocenestructure, and thus generates a positive charge in the transition metal,while the acceptor atom A assumes a negative charge. Such aself-activation can be intramolecular or intermolecular.

This may be illustrated by the example of the preferred linkage of two Xligands to a chelate ligand, that is to say of the butadienediylderivative:

The bonding site between the transition metal M and H or substituted orunsubstituted C, in the formula example substituted C of thebutadienediyl dianion shown, is then the site of olefin insertion forthe polymerization.

EXAMPLES

All the reactions were carried out under strictly anaerobic conditionsusing Schlenk techniques or the high vacuum technique. The solvents usedwere dry and saturated with argon. Chemical shifts δ are stated in ppm,relative to the particular standard: ¹H(tetramethylsilane),¹³C(tetramethylsilane), ³¹P(85% strength H₃PO₄), ¹¹B(borontrifluoride-etherate-18.1 ppm). Negative signs denote a shift to ahigher field.

Example 1

(Bis-(trimethylsilyl)-cyclopentadiene, compound 1)

14.7 g (0.106 mol) of trimethylsilyl-cyclopentadiene (obtained fromFluka) and 150 ml of tetrahydrofuran (THF) were introduced into areaction flask and cooled to 0° C. 47.4 ml of a solution ofbutyl-lithium in n-hexane (2.3 molar; total amount 0.109 mol) were addeddropwise in the course of 20 minutes. When the addition was complete,the yellow solution was stirred for a further hour; thereafter, thecooling bath was removed. The solution was stirred for a further hour atroom temperature and then cooled to −20° C. 14.8 ml (0.117 mol) oftrimethylsilyl chloride were then added dropwise in the course of 10minutes and the reaction mixture was stirred at −10° C. for 2 hours.Thereafter, the cooling bath was removed and the reaction solution waswarmed to room temperature and subsequently stirred for a further hour.The reaction mixture was filtered through Celite; the filter was washedwith hexane and the hexane was removed from the combined filtrate invacuo. On distillation at 26° C. under 0.4 mbar, the crude product gave19 g of pure product of the compound 1 (85% of the theoretical yield).The boiling point and NMR data correspond to the literature data (J.Organometallic Chem. 29 (1971), 227; ibid. 30 (1971), C 57; J. Am. Chem.Soc. 102, (1980), 4429; J. Gen. Chem. USSR, English translation 43(1973), 1970; J. Chem. Soc., Dalton Trans. 1980, 1156)

¹H-NMR (400 MHz, C₆D₆): δ=6.74 (m, 2H), 6.43 (m, 2H), −0.04 (s, 18H).

Example 2

(Trimethylsilyl-cyclopentadienyl-dichloroborane, compound 2)

16 g (0.076 mol) of the compound 1 were introduced into a round-bottomedflask equipped with a dry ice cooling bath. 8.9 g (0.076 mol) of BCl₃were condensed at −78° C. in a Schlenk tube and then added dropwise tothe round-bottomed flask over a period of 5 minutes. The reactionmixture was warmed slowly to room temperature in the course of 1 hourand then kept at 55 to 60° C. for a further 2 hours. All the volatilecompounds were removed in vacuo (3 mm Hg=4 mbar). Subsequentdistillation at 39° C. under 0.012 mbar gave 14.1 g of the compound 2(85% of the theoretical yield). The ¹H-NMR agreed with the literaturedata and showed that a number of isomers had been prepared (cf. J.Organometallic Chem. 169 (1979), 327). ¹B-NMR (64.2 MHz, C₆D₆): δ=+31.5.

Example 3

(Dichloroboranyl-cyclopentadienyl-titanium trichloride, compound 3)

11.4 g (0.052 mol) of the compound 2 and 100 ml of methylene chloride(CH₂Cl₂) were introduced into a 250 ml Schlenk tube. This solution wascooled to −78° C., and 9.8 g (5.6 ml, 0.052 mol) of titaniumtetrachloride were added dropwise in the course of 10 minutes. Theresulting red solution was warmed slowly to room temperature and stirredfor a further 3 hours. The solvent was removed in vacuo and a dirtyyellow product was obtained. 200 ml of hexane were added to the crudesolid and the resulting yellow solution was filtered and cooledovernight in a refrigerator, 12.3 g (79% of the theoretical yield) ofyellow crystals of the compound 3 being obtained. It should be pointedout that in J. Organometallic Chem. 169 (1979), 373, 62% of thetheoretical yield was obtained, the reaction being carried out in ahydrocarbon solvent, such as petroleum ether or methylcyclohexane.

¹H-NMR (400 MHz, CD₂Cl₂): δ=7.53 (t, J=2.6 Hz, 2 H), 7.22 (t, J=2.6 Hz,2H). ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=+33.

Example 4

(Dimethylboranyl-cyclopentadienyl-titanium trichloride, compound 4)

2.37 g (0.0079 mol) of the compound 3 were dissolved in 100 ml of hexanein a round-bottomed flask. This solution was cooled to 0° C. and 4 ml ofa 2 molar solution of aluminum-trimethyl in toluene (0.008 mol) wereadded dropwise. When the addition was complete, the cooling bath wasremoved and all the volatile compounds were removed in vacuo. The yellowsolid which remained was now dissolved in pentane, solid contents werefiltered off and the clear filtrate was cooled to −78° C., 1.5 g (74% ofthe theoretical yield) of compound 4 being obtained. It should be notedthat in J. Organometallic Chem. 169 (1979), 373 a yield of 87% of thetheoretical yield is stated, tetramethyltin being used as the alkylatingagent; however, it was not possible to obtain the compound 4 in a formfree from the trimethyltin chloride formed.

¹H-NMR (400 MHz, CD₂Cl₂): δ=7.48 (t, J=2.5 Hz, 2H), 7.23 (t, J=2.5 Hz,2H), 1.17 (s, 6H). ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=+56.

Example 5

(Diphenylphosphine-cyclopentadienyl)-lithium, compound 6)

50 g (0.186 mol) of cyclopentadienyl-thallium (obtained from Fluka) wereintroduced together with 300 ml of diethyl ether into a 500 ml flask.The suspension was cooled to 0° C. and 34.2 ml (0.186 mol) ofdiphenylchlorophosphine were added dropwise in the course of 10 minutes.The suspension was then warmed to room temperature and stirred for onehour, and finally filtered through a frit. The solvent was then strippedoff in vacuo and left behind 39.5 g (85% of the theoretical yield) ofthe intermediate product diphenylphosphino-cyclopentadiene, compound 5.A content of 18.6 g (0.074 mol) of the compound 5 was then diluted withtoluene and cooled to 0° C. 33.2 ml of a 2.24 molar solution ofbutyllithium in hexane (0.074 mol) were added to this solution in thecourse of 10 minutes. After warning to room temperature and afterstirring for 2 hours, the yellow solution gave a precipitate, which wasfiltered off and washed with toluene and then with hexane. After dryingin vacuo, 13.2 g of the compound 6 (70% of the theoretical yield) wereobtained as a brownish powder (cf. J. Am. Chem. Soc. 105 (1983), 3882;Organometallics 1 (1982), 1591).

¹H-NMR (400 MHz, d₈TBF): δ=7.3 (m, 4H), 7.15 (m, 6H), 5.96 (m, 2H), 5.92(m, 2H), ³¹P-NMR (161.9 MHz, d₈THF): δ=−20.

Example 6

((C₆H₅)₂P B(CH₃)₂-bridged bis-(cyclopentadienyl)-titanium dichloride,compound 7)

0.36 g (0.00139 mol) of the compound 6 and 20 ml of toluene wereintroduced into a round-bottomed flask. The solution formed was cooledto −20° C. and a solution of 0.36 g (0.00139 mol) of the compound 4 in20 ml of toluene was added dropwise in the course of 20 minutes. Whenthe dropwise addition had ended, the solution was heated to roomtemperature in the course of 2 hours and stirred at this temperature foran additional hour. Undissolved material was removed over a frit and thesolvent was distilled off in vacuo. The red oily solid was then washedwith hexane, which was decanted off, and the solid was dried again invacuo. 0.28 g (42% of the theoretical yield) of the compound 7 wasobtained as a red powder by this procedure.

¹H-NMR (300 MHz, CD₂Cl₂): δ=7.6-7.3 (br, m, 10H), 6.92 (m, 2H), 6.77 (m,4H), 6.60 (m, 2H), 0.29 (d, J_(PH)=19 Hz, 6H); ³¹P-NMR (161.9 MHz,CD₂C₂):=17.1 (br); ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=−29 (br).

Example 7

(Tributylstannyl-diphenylphosphino-indene, compound 8)

10 g (0.086 mol) of indene were introduced into a round-bottomed flask,diluted with 200 ml of diethyl ether and cooled to −20° C. 36 ml of a2.36 molar solution of butyl-lithium (0.085 mol) in n-hexane were addedto this solution, the solution immediately assuming a yellow color. Thecooling bath was removed and the reaction mixture was allowed to warm toroom temperature and was stirred for a further hour. Thereafter, thereaction mixture was cooled again to 0° C. and 19 g (15.9 ml, 0.086 mol)of diphenylchlorophosphine were added, a precipitate being formed. Thecooling bath was removed again and the solution was allowed to warm toroom temperature while being subsequently stirred for a further hour.The solution was then cooled again to −20° C. and 36 ml (0.085 mol) ofbutyl-lithium in n-hexane were added dropwise. When the addition hadended, the cooling bath was removed again and the temperature rose toroom temperature; the solution was subsequently stirred for a further1.5 hours. The suspension was then cooled again to 0° C. and 28 g (0.086mol) of tributyltin chloride were added dropwise. The resultingsuspension was warmed to room temperature and stirred for a further 1.5hours and subsequently filtered through a frit, and the solvent wasremoved in vacuo. 46.9 g of the compound 8 (92% of the theoreticalyield) remained as a heavy yellow oil.

¹H-NMR (400 MHz, CDCl₃): δ=7.5-7.3 (m, 6H), 7.28 (brs, 6H), 7.14(pseudo-d t, 7.3 Hz/1.0 Hz, 1H), 7.08 (t, J=7.3 Hz, 1H), 6.5 (br m, 1H),4.24 (br s, 1H), 1.4-1.25 (m, 6H), 1.25-1.15 (m, 6H), 0.82 (t, J=7.2 Hz,9H), 0.53 (t, J=8 Hz, 6H), ³¹P-NMR (161.9 MHz, CDCl₃): δ=−20.6.

Example 8

(Diphenylphosphino-indenyl-zirconium trichloride, compound 9)

A solution of 37 g (0.0628 mol) of the compound 8 in 300 ml of toluenewas added to a suspension of 14.6 g of ZrCl₄ (99.9% pure, 0.0628 mol,obtained from Aldrich) in 100 ml of toluene at room temperature in thecourse of 3 hours. The solution immediately became red and slowlychanged into orange and finally into yellow. After subsequently stirringfor 4 hours, the yellow precipitate was filtered off and washed withtoluene and then with hexane. The solid was dried in vacuo and gave 15.3g (50% of the theoretical yield) of the compound 9 as a free-flowingyellow powder. The yield could easily be increased to more than 70% bycarrying out the reaction at a lower temperature, for example 30 minutesat −30° C. and 5 hours at 0° C. The product could be purified further bywashing out residual tin compound using pentane in a Soxhlet extractor(extraction time: 8 hours).

Example 9

((C₆H₅)₂P BCl₂-bridged indenyl-cyclopentadienylzirconium dichloride,compound 10)

4.43 g (0.0089 mol) of the purified compound 9 and 100 ml of toluenewere introduced into a Schlenk tube. 1.95 g (0.0089 mol) of the compound2 were added to this suspension. The yellow suspension was stirred atroom temperature for 6 hours; during this period, a pale whiteprecipitate formed. This precipitate (4.1 g, 75% of the theoreticalyield) was isolated by filtration and found to be essentially purematerial.

¹H-NMR (500 MHz, CD₂Cl₂): δ=7.86 (pseudo ddd, J=8.5/2.5/1 Hz, 1H),7.75-7.55 (m, 10H), 7.35 (pseudo ddd, J=8.5/6.9/0.9 Hz, 1H), 7.32 (br t,J=3.1 Hz, 1H), 7.22 (pseudo ddd, J=8.8/6.8/1.1 Hz, 1H), 7.06 (pseudoddd, J=3.4/3.4/0.8 Hz, 1H), 6.92 (m, 1H), 6.72 (m, 1H), 6.70 (br m, 1H),6.61 (pseudo q, J=2.3 Hz, 1 H), 6.53 (br d, 8.7 Hz, 1H); ³¹P-NMR (161.9MHz CD₂Cl₂):=6.2 (br, m); ¹¹B-NMR (64.2 Mz, CD₂Cl₂): δ=−18 (br).

Example 10

((C₆H₅)₂P B(CH₃)₂-bridged indenyl-cyclopentadienylzirconium dichloride,compound 11)

50 ml of toluene were added to 1.5 g (0.00247 mol) of compound 10 fromExample 9. The suspension was cooled to 0° C. and 1.2 ml of a 2 molarsolution of trimethylaluminum in hexane (0.0024 mol) were added dropwisein the course of 5 minutes. When the addition was complete, the coolingbath was removed and the solution was allowed to warm up to roomtemperature and was further stirred for 2 hours. The remainingprecipitate was filtered off and the solvent was stripped off from thefiltrate in vacuo, 0.37 g (26% of the theoretical yield) of the compound11 remaining as a brownish solid.

³¹P-NMR (161.9 MHz, CD₂Cl₂): δ=14.6; ¹B-NMR (64.2 MHz, CD₂Cl₂):=−28

Example 11

(Trimethylsilyl-indene, compound 12)

25 ml of indene (0.213 mol, distilled over CaH₂ in vacuo) wereintroduced into a round-bottomed flask which contained 100 ml of THF andwas cooled to 0° C. 94 ml of a 2.3 molar solution of butyl-lithium inhexane (0.216 mol) were added in the course of 20 minutes. When theaddition was complete, the mixture was stirred for 20 minutes and thenwarmed to room temperature and stirred for a further 30 minutes. Aftercooling to −20° C., 27.5 ml (0.216 mol) of trimethylchlorosilane wereadded dropwise, a slightly cloudy orange-colored solution being formed.After stirring at −10° C. for 1 hour and at 0° C. for 1.5 hours, thesolution was warmed to room temperature and the solvent was removed invacuo. After dissolving again in hexane, LiCl was filtered off and thehexane was removed in vacuo. Distillation of the product (0.045 mbar, 58to 60° C.) gave 26.6 g (66% of the theoretical yield) of 12.

¹H-NMR (400 MHz, CDCl₃): δ=7.49 (t, J=7.6 Hz, 1 H), 7.28 (ddd,J=7.3/7.2/1 Hz, 1 H), 7.21 (ddd, J=7.3/7.3/1.1 Hz, 1 H), 6.96 (dd,J=5.6/1.2 Hz, 1 H), 6.69 (dd, J=5.3/1.8 Hz, 1 H), 3.56 (s, 1 H), 0.0 (s,9 H).

Example 12

(Bis-(trimethylsilyl)-indene, compound 13)

25.4 g (0.135 mol) of the compound 12 were introduced into around-bottomed flask which contained 100 ml of THF and was cooled to 0°C. 59 ml of a 2.3 molar solution of butyl-lithium in hexane (0.136 mol)were added in the course of 20 minutes. When the addition was complete,the mixture was stirred for 20 minutes and then warmed to roomtemperature. After stirring for 30 minutes, it was cooled to −20° C. and17.3 ml of trimethylchlorosilane (0.136 mol) were added dropwise, aslightly cloudy orange-colored solution being formed. The solution wasstirred at 0° C. for 1 hour and at room temperature for 1 hour and thesolvent was then removed in vacuo. After redissolving in hexane, LiClwas filtered off and the hexane was removed in vacuo. 32 g (90% of thetheoretical yield) of 13 were obtained as an oil. Cf. J. Organometal.Chem. 23 (1970), 407; hexane there instead of THF.

¹H-NMR (400 MHz, CDCl₃): δ=7.62 (d, J=7.6 Hz, 1 H), 7.52 (d, J=7.5 Hz, 1H), 7.23 (ddd, J=7.35/7.3/0.9 Hz, 1 H), 6.9 (d, J=1.7 Hz, 1 H), 3.67 (d,J=1.6 Hz, 1 H), 0.38 (s, 9 H), 0.0 (s, 9 H).

Example 13

(Trimethylsilyl-dichloroboranyl-indene, compound 14)

In a manner similar to the preparation of compound 2, 12.3 g (0.047 mol)of compound 13 were introduced into a round-bottomed flask which wascooled to −30° C. and had a reflux condenser cooled with dry ice. 5.6 g(0.046 mol) of BCl₃ were added to this. When the addition was complete,the cooling bath was removed and the reaction mixture warmed to roomtemperature and was stirred for 3 hours. The temperature was then raisedto 55° C. for 6 hours. After cooling and removal of the volatilecontents in vacuo, the crude product was obtained. Distillation under ahigh vacuum gave the purified product, the main isomer of which wasidentified as follows:

¹H-NMR (200 MHz, CDCl₃): δ=8.3 (d, J=7 Hz, 1 H), 8.1 (d, J=1.8 Hz, 1 H),

7.5 (dd, J=7.0/1.2 Hz, 1 H), 7.4 (m, 3 H), 4.0 (d, J=1.8 Hz, 1 H), 0.1(s, 9 H); ¹¹B-NMR (64.2 MHz, CD₂Cl₂): δ=38 (br).

Example 14

((C₆H₅)₂P-BCl₂-bridged bis-(indenyl)-zirconium dichloride, compound 15)

4.5 g of the compound 14 (0.017 mol) were added to a suspension of 8.3 gof compound 9 (0.017 mol) into 200 ml of toluene; the mixture was heatedto 50° C. and stirred for 5 hours. After cooling and filtration, 200 mlof hexane were added, after which a precipitate precipitated out of theclear yellow solution and was filtered off and dried in vacuo. Theproduct was identified as the meso-isomer of 15 according to its X-rayanalysis. The P→B bond length of the bridge was determined as 2.01 Å. Asecond precipitate, which was determined as the racemic isomer of 15,was obtained by concentration of the toluene/hexane solution to about 10ml and further addition of 200 ml of hexane.

Example 15

(N,N-Dimethyl-O-(methylsulfonyl)-hydroxylamine, compound 16)

(CH₃)₂NOSO₂CH₃  16

9.0 g of N,N-dimethyl-O-hydroxylamine hydrochloride (0.092 mol) weresuspended in 70 ml of CH₂Cl₂ which contained 20 g of triethylamine (0.2mol), and the suspension was cooled to −10° C. 9.5 g of methylsulfonylchloride (0.083 mol), dissolved in 70 ml of CH₂Cl₂, were slowly addeddropwise to the cooled suspension. When the addition was complete, themixture was subsequently stirred for 1 hour. Thereafter, ice-water wasadded to the reaction mixture and the organic phase was separated off.The water which remained was washed with ether. The wash ether and theCH₂Cl₂ fraction were combined and dried over Na₂SO₄ and the solventswere removed in vacuo at −10° C. 5.9 g (46% of the theoretical yield) ofcompound 16 remained as an oil, which was stored at −20° C. Cf. Angew.Chem. International Edition English 17 (1978), 687.

¹H-NMR (400 MHz, CDCl₃): δ=3.03 (s, 3H), 2.84 (s, 6H).

Example 16

(N,N-Dimethylamino-cyclopentadienyl-lithium, compound 17)

A solution of 3 g of cyclopentadienyl-lithium (0.042 mol) in 30 ml ofTHF was slowly added to a solution of 5.9 g of the compound 16 (0.042mol) in 20 ml of THF at −30° C. The mixture was then warmed to −20° C.and stirred for 30 minutes. Hexane was then added and the solution wasfiltered. Thereafter, 1.8 ml of a 2.3 molar solution of butyl-lithium(0.042 mol) in hexane were added at −20° C., whereupon a precipitateformed. The precipitate was filtered off and washed twice with 20 ml ofhexane each time. After drying in vacuo, 2.0 g (40% of the theoreticalyield) of the compound 17 were obtained as a white powder. Cf. Angew.Chem. International Edition English 19 (1980), 1010.

¹H-NMR (400 MHz, THF): δ=5.34 (br d, J=2.2 Hz, 2H), 5.15 (br d, J=2.2Hz, 2H), 2.56 (s, 6H).

Example 17

((CH₃)₂N-B(CH₃)₂-bridged bis-(cyclopentadienyl)-titanium dichloride,compound 18)

A solution of 0.18 g of the compound 4 (0.7 mmol) in 10 ml of toluenewas added to a suspension of 0.081 g of the compound 17 (0.7 mmol) in 10ml of toluene at −20° C. in the course of 10 minutes, a deep redsolution being formed. After warming at room temperature for 2 hours,the solution was filtered and the solvent was removed in vacuo. Afterthe red powder formed had been redissolved in 10 ml of warm toluene andinsoluble material had been filtered off, the solution was storedovernight in a refrigerator, 0.1 g (43% of the theoretical yield) beingformed as red needles.

¹H-NMR (400 MHz, CD₂Cl₂): δ=6.85 (t, J=2.3 Hz, 2H), 6.15 (t, J=2.3 Hz,2H), 6.1 (t, J=2.8 Hz, 2H), 5.57 (t, J=2.8 Hz, 2H), 1.98 (s, 6H), 0.35(s, 6H); ¹¹B-NNR (64.2 MHz, CD₂Cl₂): δ=2.8 (br).

Example 18

(Tributylstannyl-diisopropylphosphine-indene, compound 19)

100 ml of ether were introduced into a round-bottomed flask whichcontained 3.8 g (0.033 mol) of indene; the mixture was cooled to −20° C.14.4 ml of a 2.3 molar solution of butyl-lithium in hexane (0.033 mol)were added to this solution in the course of 5 minutes, a yellowsolution being formed. After removal of the cooling bath, the solutionwas warmed to room temperature and subsequently stirred for 1.5 hours.Thereafter, the reaction mixture was cooled to 0° C. and 5.0 g ofchlorodiisopropylphosphine (0.033 mol) were added, whereupon aprecipitate formed. After removal of the cooling bath, the solution waswarmed to room temperature and stirred for 1 hour. Thereafter, thesolution was cooled to −20° C. and 14.4 ml of a 2.3 molar solution ofbutyl-lithium in hexane (0.033 mol) were added dropwise. When theaddition was complete, the cooling bath was removed and the solution waswarmed slowly to room temperature and subsequently stirred for 1.5hours. After the suspension had been cooled to 0° C., 10.1 g ofchlorotributyltin (0.031 mol) were added dropwise. The suspension formedwas warmed to room temperature and stirred for 1.5 hours. The ether wasremoved in vacuo and the crude product was dissolved again in hexane,the solution was filtered and the filtrate was dried in vacuo, 16.6 g ofthe compound 19 (yield: 97%) remaining as a heavy yellow oil. Twoisomers were obtained in a ratio of 1.5:1. The main isomer wasidentified as follows: ¹H-NMR (400 MHz, CD₂Cl₂): δ7.71 (d, J=7.2 Hz, 1H), 7.41 (d, J=7.3 Hz, 1 H), 7.13 (m, 2 H), 6.96 (m, 1 H), 4.28 (s withSn satellites, 1 H), 2.21 (m, 1 H), 1.54 (m, 1 H), 1.45-0.65 (m, 39 H).³¹P-NMR (161.9 MHz, CD₂Cl₂): δ−11.3 ppm. The secondary isomer wasidentified as follows: ¹H-NMR (400 MHz, CD₂Cl₂) δ7.6 (d, J 7.4 Hz, 1 H),7.46 (d, J=7.2 Hz, 1 H), 7.26 (t, J=7.5 Hz, 1 H), 7.1 (m, 1 H), 6.71 (m,1 H), 3.48 (m, 1 H), 2.21 (m, 1 H), 1.54 (m, 1 H), 1.45-0.65 (m, 39 H).³¹P-NMR (161.9 MHz, CD₂Cl₂): d−11.5 ppm.

Example 19

(Diisopropylphosphino-indenyl-zirconium trichloride, compound 20)

A solution of 15.0 g of the compound 19 (0.029 mol) in 50 ml of toluenewas added dropwise to a suspension of 6.7 g (0.029 mol) of 99.9% pureZrCl₄ in 300 ml of toluene at −78° C. When the addition was complete,the reaction mixture was stirred at −30° C. for 0.5 hour and then at 0°C. for 4 hours. The yellow precipitate which formed was filtered off andwashed with toluene and hexane. The solids were dried in vacuo, 8.8 g ofthe compound 20 (yield: 71%) remaining as a free-flowing yellow powder.The powder was further purified by removal of the remaining tincompounds by means of extraction with toluene fed under reflux over aperiod of 3 hours under 30 mm Hg and then with pentane over a period of2 hours in a Soxhlet extractor. Because of the insolubility of thecompound formed, no ¹H-NMR was obtained.

Example 20

(Diisopropylphosphino-dichloroboranyl-bridgedindenyl-cyclopentadienyl-zirconium dichloride, compound 21)

0.52 g (0.0012 mol) of the compound 20 and 30 ml of toluene wereintroduced into a Schlenk tube. 0.27 g (0.0012 mol) of the compound 2were added to this suspension in the course of 5 minutes. The yellowsuspension was stirred at room temperature for 3 hours, a slightlycloudy solution remaining. The precipitate was removed by filtration, apale yellow toluene solution remaining. After removal of the toluene invacuo, the product remained as a whitish solid in an amount of 0.47 g(yield: 87%). ¹H-NMR (400 MHz, CD₂Cl₂) δ 7.84 (pseudo dd, J=8.5, 0.8 Hz,1 H), 7.73 (d, J=8.8 Hz, 1 H), 7.5 (pseudo dt, J=7.8, 0.8 Hz, 1 H), 7.38(m, 2 H), 6.98 (m, 1 H), 6.67 (m, 1 H), 6.64 (m, 1 H), 6.54 (m, 1 H),6.29 (m, 1 H), 3.39 (septet, J=7.1 Hz, 1 H), 2.94 (m, 1 H), 1.68 (dd,J_(H-P)=18.1 Hz, J=7.2 Hz, 3 H), 1.64 (dd, J_(H-P)=17.4, J=7.2 Hz, 3 H),1.45 (dd, J_(H-P)=15 Hz, J=7.2 Hz, 3 H), 1.33 (dd, J_(H-P)=14.6 Hz,J=7.3 Hz, 3 H). 31P-NMR (161.9 MHz, CD₂Cl₂): δ 23.1 (br, m); ¹¹B-NMR (80MHz, CD₂Cl₂): δ 14.8 (br d, J=110 Hz).

Example 21

(Tributylstannyl-dimethylphosphino-indene, compound 22)

150 ml of ether were introduced into a round-bottomed flask whichcontained 5.5 g (0.047 mol) of indene; the mixture was cooled to −20° C.20.8 ml of a 2.3 molar solution of butyl-lithium in hexane (0.048 mol)were added to this solution in the course of 5 minutes, a yellowsolution being formed. After removal of the cooling bath, the solutionwas warmed to room temperature and subsequently stirred for 1 hour.After the reaction mixture had been cooled to −30° C., 4.6 g ofchlorodimethylphosphine (0.048 mol) in 30 ml of ether were added in thecourse of 20 minutes, a precipitate forming. After stirring at −20° C.for 2 hours, 20.8 ml of a 2.3 molar solution of butyl-lithium in hexane(0.048 mol) were added dropwise. When the addition was complete, thecooling bath was removed and the solution was warmed slowly to roomtemperature and subsequently stirred for 1.5 hours. After the suspensionhad been cooled to 0° C., 15.6 g of chlorotributyltin (0.048 mol) wereadded dropwise. The suspension formed was warmed to room temperature andstirred for 1.5 hours. The ether was removed in vacuo and the crudeproduct was dissolved again in hexane, the solution was filtered and thefiltrate was dried in vacuo, 17.4 g of the compound 22 (yield: 78%)remaining as a heavy yellow oil. ¹H-NMR (400 MHz, CD₂Cl₂) δ 7.67 (d,J=7.5 Hz, 1 H), 7.47 (d, J=7.4 Hz, 1 H), 7.18 (m, 2 H), 6.83 (m, 1 H),4.28 (s with Sn satellites, 1 H), 1.43-0.78 (m, 33 H). ³¹P-NMR (161.9MHz, CD₂Cl₂): δ−61.6 ppm.

Example 22

(Dimethylphosphino-indenyl-zirconium trichloride, compound 23)

A solution of 17.0 g of the compound 22 (0.037 mol) in 50 ml of toluenewas added to a suspension of 8.5 g (0.036 mol) of 99.9% pure ZrCl₄ in200 ml of toluene at −78° C. When the addition was complete, thereaction mixture was stirred at −30° C. for 0.5 hour and then at 0° C.for 4 hours. The yellow precipitate formed was filtered off and washedwith toluene and hexane. The solids were dried in vacuo, 8.3 g of thecompound 23 (yield: 61%) remaining as a free-flowing yellow powder. Thepowder was further purified by removal of the remaining tin compounds bymeans of extraction with toluene fed under reflux over a period of 3hours under 30 mm Hg and then with pentane over a period of 2 hours in aSoxhlet extractor, 7.2 g (yield: 53%) of the product remaining. Becauseof the insolubility of this compound, no ¹H-NMR was obtained.

Example 23

(Dimethylphosphino-dichloroboranyl-bridgedindenyl-cyclopentadienyl-zirconium dichloride, compound 24)

30 ml of toluene and 0.55 g of the compound 23 (0.0015 mol) wereintroduced into a Schlenk tube. 0.31 g (0.0014 mol) of the compound 2were added to this suspension in the course of 5 minutes. The yellowsuspension was stirred at room temperature for 6.5 hours, a slightlycloudy solution remaining. The precipitate was removed by filtration, apale yellow toluene solution remaining. After removal of the toluene invacuo, the product remained as a whitish solid. After the product hadbeen washed with hexane and dried in vacuo, the compound 24 remained asa pale white solid (0.54 g; yield: 76%). ¹H-NMR (400 MHz, CD₂Cl₂) δ 7.84(pseudo dd, J=7.4 Hz 1.0 Hz, 1 H), 7.60 (m, 2 H), 7.51 (m, 1 H), 7.38(m, 1 H), 6.93 (m, 1 H), 6.71 (m, 1 H), 6.66 (m, 1 H), 6.49 (m, 1 H),6.30 (br s, 1 H), 2.11 (d J_(H-P)=11.9 Hz, 3 H), 1.94 (d, J_(H-P)=11.9Hz, 3 H). ³¹P-NMR (161.9 MHz, CD₂Cl₂)−5.9 (br, m); ¹¹B-NMR (80 MHz,CD₂Cl₂) δ−14.6 (br d, J_(B-P)=126 Hz).

Example 24

(2-Methylindene, compound 26)

38.7 g (0.29 mol) of 2-indanone and 300 ml of ether were introduced intoa round-bottomed flask. 96.7 ml of a 3.0 molar solution of CH₃MgI inether (0.29 mol), which was diluted with 150 ml of ether, wereintroduced into a second flask. Thereafter, the 2-indanone solution wasadded to the CH₃MgI solution via a cannula in an amount such that thereflux was maintained, a precipitate being formed. When the addition wascomplete, the suspension was kept under reflux for a further 4 hours andcooled to 0° C., after which 100 ml of a saturated solution of NH₄Clwere slowly added. The product was extracted with ether and dried overMgSO₄. After removal of the solvent in vacuo, 30.1 g (yield: 70%) of2-methyl-2-indanol (compound 25) were obtained as an oily solid. ¹H-NMR(400 MHz, CDCl₃) δ 7.15 (br m, 4 H), 3.01 (s, 2 H), 2.99 (s, 2 H), 1.5(s, 3 H); OH variable.

25.5 g (0.17 mol) of the compound 25, 3.2 g (0.017 mol) ofp-toluenesulfonic acid and 500 ml of hexane were introduced into around-bottomed flask with a Dean-Stark collecting vessel. Thissuspension was kept under reflux for 3 hours. After cooling, the hexanefraction was decanted from the insoluble products and the solvent wasremoved in vacuo to leave an oil which was then distilled in a shortdistillation column at 45° C. under 0.03 mbar, whereupon 15 g (yield:68%) of the compound 26 were obtained. ¹H-NMR (400 MHz, CDCl₃) δ 7.33(d, J=7.6 Hz, 1 H), 7.21 (m, 2 H), 7.06 (pseudo d t, J=7.2, 1.4 Hz, 1H), 6.45 (br s, 1 H), 3.25 (s, 2 H), 2.12 (s, 3 H).

Reference is made to:

1. Morrison, H; Giacherio, D. J. Org. Chem. 1982, 47, 1058.

2. Ready, T. E.; Chien, J. C. W.; Rausch, M. D. J. Organorn. Chem. 591,1996, 21.

3. Wilt, Pawlikowki, Wieczorek J. Org. Chem. 37, 1972, 824.

Example 25

(Tributylstannyl-diisopropylphosphino-2-methylindene, compound 27)

150 ml of ether were introduced into a round-bottomed flask whichcontained 5.08 g (0.039 mol) of 2-methylindene 26; the mixture wascooled to −20° C. 17.0 ml of a 2.3 molar solution of butyl-lithium inhexane (0.039 mol) were added to this solution in the course of 5minutes, a yellow solution being formed. After removal of the coolingbath, the solution was warmed to room temperature and subsequentlystirred for 1 hour. Thereafter, the reaction mixture was cooled to −20°C. and 5.8 g (0.039 mol) of chlorodiisopropylphosphine were added in thecourse of 5 minutes, a precipitate being formed. Thereafter, the coolingbath was removed and the reaction mixture was stirred at roomtemperature for 1 hour. After cooling to −20° C., 17.0 ml of a 2.3 molarsolution of butyl-lithium in hexane (0.039 mol) were added dropwise.When the addition was complete, the cooling bath was removed and thesolution was warmed slowly to room temperature and subsequently stirredfor 1.5 hours. After the suspension had been cooled to 0° C., 12.4 g(0.038 mol) of chlorotributyltin were added dropwise. The suspensionformed was heated to room temperature and stirred for 1.5 hours. Theether was removed in vacuo and the crude product was dissolved again inhexane, the solution was filtered and the filtrate was dried in vacuo,20.4 g (yield: 98%) of the compound 27 remaining as a heavy yellow oil.Two isomers were identified by ³¹P-NMR. ³¹P-NMR (161.9 MHz, CD₂Cl₂)δ−5.9 and −6.6 in a ratio of 2:1.

Example 26

(Diisopropylphosphino-2-methylindenyl-zirconium trichloride, compound28)

A solution of 17.7 g (0.033 mol) of the compound 27 in 100 ml ofmethylene chloride was added to a suspension of 7.7 g (0.033 mol) of99.9% pure ZrCl₄ in 200 ml of methylene chloride at −25° C. in thecourse of 10 minutes. When the addition was complete, the reactionmixture was warmed slowly to 10° C. over a period of 3 hours, afterwhich a clear, orange-colored solution was formed. After 1 hour at roomtemperature, the solvent was removed in vacuo and the oil formed waswashed with 2×50 ml of hexane, whereupon an oily crude product (28) wasobtained, this being used directly for the preparation of the compound29. Because of the insolubility of this compound, no ¹H-NMR wasobtained.

Example 27

(Diisopropylphosphino-dichloroboranyl-bridged2-methylindenyl-cyclopentadienyl-zirconium dichloride, compound 29)

5.5 g (0.025 mol) of the compound 2 were introduced into around-bottomed flask which contained 0.025 mol of the impure compound 28in 200 ml of toluene at 0° C., over a period of 5 minutes. After 1 hourat 0° C., the stirring was ended and the soluble toluene fraction wasdecanted from the oil formed. After removal of the toluene in vacuo, 100ml of hexane were added to the oily solid, 7.4 g (yield: 54%) of ayellow powder being formed with a purity of about 90%. The product wasfurther purified in a Soxhlet extraction apparatus with pentane fedunder reflux. The end product comprised a pale yellow powder. ¹H-NMR(400 Mrz, CD₂Cl₂) δ 8.67 (br d, J=7.6 Hz, 1 H), 7.71 (m, 1 H), 7.35 (m,2 H), 6.62 (br s, 1 H), 6.54 (br s, 1 H), 6.47 (m, 1 H), 6.33 (m, 1 H),6.06 (br s, 1 H), 3.3 (br m, 1 H), 3.2 (br m, 1 H), 2.6 (s, 3 H), 1.78(dd, J=7.1 Hz, J_(H-P)=15.3 Hz, 3 H), 1.70 (dd, J=7.2 Hz, J_(H-P)=15.7Hz, 3 H). 1.57 (dd, J=7.1 Hz, H_(H-P)=15.3 Hz, 3 H), 1.12 (dd, J=7.1 Hz,J_(H-P)=14.0 Hz, 3H). 31P-NMR (161.9 MHz, CD₂Cl₂) 28.4 (br m); ¹B-NMR(80 MHz, CD₂Cl₂) δ−14.3 (br d, J_(P-B)=106 Hz).

Example 28

(Bis(trimethylsilyl)-diphenylphosphino)-cyclopentadiene, compound 30)

76.6 ml of a 2.5 molar solution of butyl-lithium in hexane (0.19 mol)were added to a solution of the compound 1 (40.2 g; 0.19 mol) in 500 mlof ether at 0° C. in the course of 10 minutes. When the addition wascomplete, the bath was removed and the solution was stirred at roomtemperature for 1 hour. After cooling to 0° C., 42.2 g (0.19 mol) ofchlorodiphenylphosphine were added in the course of 10 minutes, afterwhich the bath was removed and the suspension was warmed to roomtemperature. After stirring at room temperature for 1 hour, the etherwas removed in vacuo and the product was dissolved again in hexane.After the salts had been filtered off, the hexane was removed in vacuo,69.1 g (yield. 91%) of the compound 30 remaining as an oil. ¹H-NMR (400MHz, CDCl₃) δ 7.45 (m, 4H), 7.35 (m, 6H), 6.8 (m, 1 H), 6.65 (m, 1 H),6.6 (m, 1H), 0 (s 18 H). ³¹P-NMR (161.9 MHz, CDCl₃): δ−19.5 ppm.

Example 29

(Trimethylsilyl-diphenylphosphino-cyclopentadienyl-zirconiumtrichloride, compound 31)

A solution of the compound 30 (69.1 g, 0.175 mol) in 200 ml of methylenechloride was added to a suspension of 41.5 g (0.178 mol) of 99.9% pureZrCl₄ in 200 ml of methylene chloride via a cannula and the mixture wasstirred at room temperature for 8 hours. During this period, thesolution became cloudy. The solids were filtered off, washed with 2×20ml of toluene and then 2×20 ml of hexane and dried in vacuo. The productcomprised 35 g (yield: 39%) of a pale yellow powder. Because of theinsolubility of the product, no ¹H-NMR was obtained.

Example 30

(Diphenylphosphino-dichloroboranyl-bridgedtrimethylsilylcyclopentadienyl-cyclopentadienyl-zirconium dichloride,compound 32)

A solution of the compound 2 (2.6 g, 0.012 mol) was added to asuspension of the compound 31 (5.6 g, 0.011 mol) in 100 ml of toluene at0° C. After the mixture had been stirred at 0° C. for 5 hours, theyellow-brown solid was removed by filtration, a whitish solutionremaining. After removal of the toluene in vacuo and washing of thesolid which remained with pentane, the compound 32 remained as a highlyair-sensitive whitish powder (5.5 g; yield: 81%). ¹H-NMR (400 MHz,CD₂Cl₂) δ: 7.8-7.5 (m, 10 H), 7.06 (m, 1 H), 6.92 (m, 1 H), 6.83 (m, 1H), 6.75 (m, 2 H), 6.68 (m, 1 H), 6.63 (m, 1 H), 0.26 (s, 9 H). ³¹P-NMR(161.9 MHz, CD₂Cl₂) δ: 0 (br, m); ¹¹B-NMR (80 MHz, CD₂Cl₂) δ−16.3 (br d,J_(B-P)=82 Hz).

Example 31

(Diisopropylphosphino-cyclopentadienyl-lithium, compound 33)

50 ml of ether were introduced into a round-bottomed flask whichcontained 1.68 g (0.023 mol) of cyclopentadienyl-lithium. After thereaction flask had been cooled to −20° C., 3.6 g (0.023 mol) ofchlorodiisopropylphosphine were added dropwise. When the addition wascomplete, the cooling bath was warmed to 0° C. and the reaction mixturewas stirred for 1 hour. Thereafter, ether was removed in vacuo, theproduct was dissolved in toluene and the solution was filtered. Afterthe frit had been rinsed through with 2×10 ml of toluene, the reactionmixture was cooled to −20° C. and 9.3 ml of a 2.5 molar solution ofbutyllithium in hexane (0.023 mol) were added, an orange-coloredsolution being formed. A small fraction was taken for NMR analysis and,after removal of the toluene in vacuo and washing of the oil formed withhexane, a pale yellow solid (33) was obtained. ¹H-NMR (400 MHz, THF) δ:5.89 (m, 2 H), 5.83 (br s, 2 H), 1.86 (m, 2 H), 1.0-0.8 (m, 12 H). Themain amount was used directly for the preparation of the compound 34.

Example 32

(Diisopropylphosphino-dimethylboranyl-bridgedbis-cyclopentadienyl-titanium dichloride, compound 34)

A solution of 6.1 g (0.023 mol) of the compound 4 in 50 ml of toluenewas added to a toluene solution of the compound 33 (0.023 mol) from theabovementioned reaction at −78° C. After the mixture had been stirred at−78° C. for 30 minutes, the cooling bath was removed and the solutionwas subsequently stirred at room temperature for 2 hours. Thereafter,the solids were removed by filtration and the toluene was removed invacuo. Hexane was then added to the red oily product, a red powder beingformed, which was filtered off, washed with 2×20 ml of hexane and driedin vacuo, whereupon the compound 34 was formed as a red powder (5.95 g,yield, based on CpLi: 61%). ¹H-NMR (400 MHz, CD₂Cl₂) δ: 6.96 (m, 2 H),6.94 (pseudo t, J=2.4 Hz, 2 H), 6.59 (m, 2 H), 6.42 (m, 2 H), 2.58 (m, 2H), 1.44 (dd, J=7.3 Hz, J_(H-P)=14.7 Hz, 6 H), 1.27 (dd, J=7.2 Hz,J_(H-P)=13.1 Hz, 6 H), 0.31 (d, J_(H-P)=16.4 Hz, 6 H). ³¹P-NMR (161.9MHz, CD₂Cl₂) δ 28.7 (br m); ¹¹B-NMR (80 MHz, CD₂Cl₂) δ−29.7 (br m).

Example 33

(Dimethylphosphino-tributylstannyl-2-methylindene, compound 35)

100 ml of ether were introduced into a round-bottomed flask whichcontained 6.76 g (0.052 mol) of 2-methylindene (compound 26); themixture was cooled to −20° C. 21 ml of a 2.5 molar solution ofbutyl-lithium in hexane (0.052 mol) were added to this solution in thecourse of 5 minutes, a yellow solution being formed. After removal ofthe cooling bath, the solution was warmed to room temperature andsubsequently stirred for 1 hour. After the reaction mixture had beencooled to −20° C., 5.0 g (0.052 mol) of chlorodimethylphosphine wereadded in the course of 5 minutes, a precipitate being formed. Thecooling bath was then removed and the reaction mixture was stirred atroom temperature for 1 hour. After cooling to −20° C., 21.0 ml of a 2.5molar solution of butyl-lithium in hexane (0.052 mol) were addeddropwise. When the addition was complete, the cooling bath was removed,after which the solution was warmed slowly to room temperature andstirred for 1.5 hours. After the suspension had been cooled to 0° C.,16.9 g (0.052 mol) of chlorotributyltin were added dropwise. Thesuspension formed was warmed to room temperature and stirred for 1.5hours. After removal of the ether in vacuo, the crude product wasdissolved again in hexane, the solution was filtered and the filtratewas dried in vacuo, 24.3 g (yield: 98%) of the compound 35 remaining asa heavy yellow oil. ³¹P-NMR (161.9 MHz, CD₂Cl₂) δ−68.5 (s).

Example 34

(Dimethylphosphino-2-methylindenyl-zirconium trichloride, compound 36)

A solution of 17.4 g (0.036 mol) of the compound 35 in 100 ml of toluenewas added to a suspension of 8.5 g (0.036 mol) of 99.9% pure ZrCl₄ in100 ml of toluene at 0° C. in the course of 10 minutes. When theaddition was complete, the reaction mixture was warmed slowly to 10° C.over a period of 1 hour and then stirred at room temperature for 6hours. The yellow precipitate was subsequently filtered off, washed with2×20 ml of toluene and 2×20 ml of hexane and dried in vacuo. The powderwas further purified by removal of the remaining tin compounds by meansof extraction with toluene fed under reflux over a period of 3 hoursunder 30 mm Hg and then with pentane over a period of 2 hours in aSoxhlet extractor, 5.8 g (yield: 41%) of the compound 36 remaining as aluminous yellow powder. Because of the insolubility of this compound, no¹H-NMR was obtained.

Example 35

(Dimethylphosphino-dichloroboranyl-bridged2-methylindenyl-cyclopentadienyl-zirconium dichloride, compound 37)

2.7 g (0.012 mol) of the compound 2 were introduced into around-bottomed flask, which contained 4.8 g (0.012 mol) of the compound36 in 125 ml of toluene at room temperature, in the course of 5 minutes.After the mixture had been stirred for 7 hours, the dark yellow solidwas filtered off, washed with 2×20 ml of hexane and dried in vacuo, 5.5g (yield: 89%) of the compound 37 being obtained as a pale yellow solid.¹H-NMR (400 MHz, CD₂Cl₂) δ 8.39 (d, J=8.5 Hz, 1 H), 7.71 (m, 1 H), 7.4(m, 2 H), 6.64 (m, 2 H), 6.46 (pseudo q, J=5.3, 2.9 Hz, 1 H), 6.37 (m, 1H), 6.08 (m, 1 H), 2.51 (s, 3 H), 2.1 (d, J_(H-P)=12 Hz, 3 H), 2.0 (d,J_(H-P)=12 Hz, 3 H); ³¹P-NMR (161.9 MHz, CD₂Cl₂) 5.3 (br m); ¹¹B-NMR (80MHz, CD₂Cl₂) δ−16.5 (br d, J_(B-P)=116 Hz).

Example 36

(Dicyclohexylboranylcyclopentadienyl-lithium, compound 39)

Reference is made to: Herberich, G. E.; Fischer, A. Organometallics1996, 15, 58.

40 ml of a 1 molar solution of chlorodicyclohexylborane in hexane (0.04mol) were added to 20 ml of cyclopentadienyl-sodium (2 M in THF; 0.04mol) in 100 ml of hexane at −78° C. After removal of the cooling bath,the reaction mixture was warmed to room temperature and stirred for 1hour. After filtration and removal of the solvent in vacuo, 9.1 g(yield: 94%) of the compound 38 remained as a yellow oil, which was useddirectly in the synthesis of the compound 39.

5.3 g (0.038 mol) of 2,2,6,6-tetramethylpiperidine were introduced intoa round-bottomed flask which contained 40 ml of THF. After cooling to−20° C. and addition of 15 ml of a 2.5 molar solution of butyl-lithiumin hexane (0.038 mol), the mixture was stirred at −20° C. for 1 hour andthen cooled to −78° C. 9.1 g (0.038 mol) of the compound 38 in 20 ml ofhexane were added to this solution in the course of 10 minutes. Thecooling bath was removed and the solution was stirred at roomtemperature for 1 hour. After removal of the solvent in vacuo andaddition of hexane, the mixture was subsequently stirred for 2 hours, awhite suspension being formed, which was filtered, and the product wasdried in vacuo. 4.6 g (yield: 50%) of the compound 39 were formed as awhite powder. ¹¹B-NMR (80 MHz, THF) δ43.9.

Example 37

(Diphenylphosphino-dicyclohexylboranyl-bridgedtrimethylsilyl-cyclopentadienyl-cyclopentadienyl-zirconium dichloride,compound 40)

After cooling a Schlenk flask which contained 1.4 g (0.0056 mol) of thecompound 39 and 2.9 g (0.0056 mol) of the compound 31 to −20° C., 100 mlof toluene were added. After removal of the bath, the suspension wasstirred at room temperature for 6 hours and then filtered. The solventwas removed in vacuo, an oily solid remaining, which was washed withhexane and filtered. After the solid had been dried in vacuo, 1.9 g(yield: 48%) of the compound 40 remained as a pink-colored solid. ¹H-NMR(400 MHz, CD₂Cl₂) δ 7.6-7.2 (br m, 10 H), 7.04 (br s, 1 H), 6.95 (m, 1H), 6.82 (m, 1 H), 6.76 (br s, 1 H), 6.66 (m, 1 H), 6.63 (m, 1 H), 6.52(m, 1 H), 1.6-1.1 (br m, 22 H), 0.26 (s, 9 H); ³¹P-NMR (161.9 MHz,CD₂Cl₂) δ 16.3; ¹¹B-NMR (80 MHz, CD₂Cl₂) δ−13.8.

Example 38

(4,7-Dimethylindene, compound 41)

Reference is made to: Erker, G. et al. Tetrahedron 1995, 51, 4347.

A 30% strength solution of 153 g (2.8 mol) of sodium methoxide inmethanol was diluted with 60 ml of methanol and cooled to 0° C. 34 g(0.52 mol) of cyclopentadiene were added to this solution. After 15minutes, 39 g (0.34 mol) of 2,5-hexanedione were added dropwise, afterwhich the cooling bath was removed and the reaction mixture was stirredat room temperature for 2 hours. 200 ml of water and 200 ml of etherwere then added. The ether layer was removed, washed with water andsodium chloride solution and then dried over Na₂SO₄. After removal ofthe solvent in vacuo and distillation at 65° C. under 0.1 mbar, thecompound 41 remained as an orange-colored oil (40 g; yield: 81%). ¹H-NMR(400 MHz, CDCl₃) δ 7.35-7.27 (m, 2 H), 7.23 (d, J=7.6 Hz, 1 H), 6.82 (m,1 H), 3.51 (s, 2 H), 2.75 (s, 3H), 2.63 (s, 3 H).

Example 39

(Diisopropylphosphino-tributylstannyl-4,7-dimethylindene, compound 42)

100 ml of ether were introduced into a round-bottomed flask whichcontained 5.0 g (0.035 mol) of 4,7-dimethylindene (compound 41); themixture was cooled to −20° C. 14 ml of a 2.5 molar solution ofbutyl-lithium in hexane (0.035 mol) were added to this solution in thecourse of 5 minutes, a yellow solution being formed. After removal ofthe cooling bath, the solution was warmed to room temperature andsubsequently stirred for 1 hour. After the reaction mixture had beencooled to −20° C., 5.3 g (0.035 mol) of chlorodiisopropylphosphine wereadded in the course of 5 minutes, a precipitate being formed.Thereafter, the cooling bath was removed and the reaction mixture wasstirred at room temperature for 1 hour. After cooling to −20° C., 14.0ml of a 2.5 molar solution of butyllithium in hexane (0.035 mol) wereadded dropwise. When the addition was complete, the cooling bath wasremoved and the solution was warmed slowly to room temperature andstirred for 1.5 hours. After the suspension had been cooled to 0° C.,11.4 g of chlorotributyltin (0.035 mol) were added dropwise. Thesuspension formed was warmed to room temperature and stirred for 1.5hours. The ether was removed in vacuo and the crude product wasdissolved again in hexane, the solution was filtered and the filtratewas concentrated in vacuo, 16 g (yield: 83%) of the compound 42remaining as a heavy yellow oil. ³¹P-NMR (161.9 MHz, CD₂C₂) δ−9 ppm.

Example 40

(Diisopropylphosphino-4,7-dimethylindenyl-zirconium trichloride,compound 43)

A solution of 16.0 g (0.029 mol) of the compound 42 in CH₂Cl₂ (100 ml)was added to a suspension of 6.4 g (0.029 mol) of 99.9% pure ZrCl₄ in100 ml of CH₂Cl₂ at −20° C. in the course of 10 minutes. When theaddition was complete, the reaction mixture was warmed slowly to roomtemperature over a period of 2 hours and then stirred at roomtemperature for a further two hours. Thereafter, the solids were removedby filtration and the solvent was removed in vacuo, the crude compound43 remaining as an oil which was used directly for the preparation ofthe compound 44.

Example 41

(Diisopropylphosphino-dichloroboranyl-bridged4,7-dimethylindenyl-cyclopentadienyl-zirconium dichloride, compound 44)

5.0 g (0.023 mol) of the compound 2 were introduced into around-bottomed flask, which contained 10.6 g (0.023 mol) of the compound43 in 125 ml of toluene at 0° C., in the course of 5 minutes. After themixture had been stirred at 0° C. for 1.5 hours, the cooling bath wasremoved and the suspension was stirred at room temperature for a further3 hours. Thereafter, the toluene-soluble fraction was decanted from theheavy oil which had formed during the reaction, and was concentrated todryness in vacuo, a heavy oil remaining. After addition of 100 ml ofhexane to this oil, the mixture was subsequently stirred and a darkyellow powder was filtered off and was dried in vacuo. After thisprocess, 6.3 g (yield: 48%) of the compound 44 remained as a dark yellowpowder. The product can be further purified by precipitation of a CH₂Cl₂solution of the compound 44 in a hydrocarbon solvent. ¹H-NMR (400 MHz,CD₂Cl₂) δ 8.03 (pseudo t, J=8.5 Hz, 1 H), 7.22 (d, J=7 Hz, 1 H), 7.08(d, J=7.1 Hz, 1 H), 7.02 (m, 1 H), 6.77 (m, 1 H), 6.70 (m, 1 H), 6.58(m, 1 H), 6.44 (br s, 1 H), 3.51 (m, 1 H), 2.82 (m, 1 H), 2.64 (s, 3 H),2.50 (s, 3 H), 1.77 (dd, J=7.2 Hz, J_(H-P)=16.3 Hz, 3 H), 1.69 (dd,J=7.1 Hz, J_(H-P)=15.2 Hz, 3 H), 1.58 (dd, J=7.1 Hz, J_(H-P)=15.5 Hz, 3H), 1.28 (dd, J=7.2 Hz, J_(H-P)=14.5 Hz, 3 H); ³¹P-NMR (161.9 MHz,CD₂Cl₂) δ 28.4 (br d, J=138 Hz); ¹¹B-NMR (80 MHz, CD₂Cl₂) δ−15.3 (d,J=107 Hz).

Example 42

(Pyrrole-lithium, compound 45)

59 ml of a solution of butyl-lithium (2.5 molar in hexane, 0.148 mol)were added slowly to a solution of 9.9 g of pyrrole (0.148 mol) in 200ml of hexane at −20° C., a white solid being formed. The mixture wassubsequently stirred at room temperature for 2 hours and the solid wasisolated by filtration, washed twice with 20 ml of hexane each time anddried in vacuo. This process gave 6 g of the compound 45 (56% of thetheoretical yield).

¹H-NMR (400 MHz, THF): δ 6.71 (s, 2H), 5.95 (s, 2H).

Example 43

(Dimethylboranyl-bridged cyclopentadienyl-pyrrole-titanium dichloride,compound 46)

A solution of 1.34 g (0.005 mol) of the compound 4 in 20 ml of toluenewas added to 0.38 g (0.005 mol) of the compound 45 at −78° C. in thecourse of 5 minutes. The cooling bath was then removed and stirring wascontinued at room temperature for 2 hours. Thereafter, the red solidwhich had formed was filtered off; the yellow filtrate was discarded.The red solid was washed with toluene and dried in vacuo. 1.14 g with asmall content of LiCl were obtained.

¹H-NMR (400 MHz, THF): δ=6.89 (pseudo-t, J=2.3 Hz, 2 H), 6.64 (m, 2 H),6.59 (pseudo-t, J=2.35 Hz, 2 H), 5.73 (pseudo-t, J=1.7 Hz, 2 H), 0.06(s, 6 H). ¹¹B-NMR (80 MHz, THF) δ=−26 ppm.

Example 44

(1-Phenyl-2,3,4,5-tetramethyl-phosphol, compound 47)

In accordance with Organometallics 7 (1988), 921, a solution of 11.7 g(0.216 mol) of 2-butine in 150 ml of CH₂Cl₂ was slowly added to 15.3 g(0.115 mol) of AlCl₃ in CH₂Cl₂ (0° C.; 30 minutes). The mixture wassubsequently stirred at 0° C. for 45 minutes, the cooling bath was thenremoved and the mixture was subsequently stirred for a further hour.Thereafter, the solution was cooled to −50° C. and a solution of 21.4 g(0.12 mol) of phenyl-dichlorophosphine in CH₂Cl₂ was added in the courseof 20 minutes. The cooling bath was then removed and the dark redsolution was subsequently stirred for one hour and then added to asolution of 27 g (0.13 mol) of tributylphosphine in 100 ml of CH₂Cl₂ at−30° C. The red color disappeared immediately; a yellow solutionremained. When the addition had ended, the solvent was removed in vacuo;a thick yellow oil remained. The oil was taken up in hexane and washedwith saturated aqueous NaHCO₃ solution and H₂O under an Ar atmosphere.After drying over MgSO₄, the hexane was removed in vacuo. 18.2 gremained as a clear oil (yield 78%). ¹H-NMR (400 MHz, CDCl₃) δ: 7.3 (m,5H), 2.0 (m, 12H), ³¹P-NMR (161.9 MHz, CDCl₃) δ: 16.8 ppm.

Example 45

(Lithium-2,3,4,5-tetramethyl-phosphol, compound 48)

In accordance with Organometallics 7 (1988), 921, 0.52 g (0.074 mol) oflithium was added to a solution of 7 g (0.032 mol) of the compound 47 in150 ml of tetrahydrofuran (THF) and the mixture was stirred overnight.The resulting red solution was filtered through a frit to removeresidual solids and the filtrate was cooled to 0° C. Thereafter, asolution of 1.45 g (0.01 mol) of AlCl₃ in 20 ml of THF was addeddropwise and the solution was brought to room temperature. An aliquotamount was removed for analysis and the remaining solution was useddirectly for the preparation of the compound 49. ³¹P-NMR (161.9 MHz,THF) δ: 63.7 ppm.

Example 46

(Dimethylboranyl-cyclopentadienyl-tetramethylphospholtitaniumdichloride, compound 49)

The THF solution from Example 45 with 1.46 g (0.01 mol) of the compound48 was introduced into a round-bottomed flask; the THF was removed invacuo. After addition of toluene and cooling to −78° C., a solution of2.6 g (0.01 mol) of the compound 44 in 20 ml of toluene was slowly addedwhile stirring, a red suspension being formed. When the addition hadended, the suspension was brought to room temperature and subsequentlystirred for 1 hour. After solid which remained undissolved had beenfiltered off, the toluene was removed in vacuo; hexane was added to theoily solid which remained. The solid which remained undissolved was alsofiltered off from the hexane solution and the solution was storedovernight at −20° C. After the hexane had been decanted off, 0.5 g of agreen solid which was identified as compound 49 (yield 14%) wasobtained. ¹H-NMR (200 MHz, CD₂Cl₂) δ: 6.64 (m, 2H), 6.57 (m, 2H), 2.11(d, J_(H-P)=10 Hz, 6H), 2.09 (s, 6H), 0.87 (d, J_(H-P)=5.3 Hz, 6H).³¹P-NMR (161.9 MHz, THE) δ: 95.6 ppm, ¹¹B-NMR (80 MHz, CD₂Cl₂) δ: 39(br, m) ppm.

Example 47

(Ethylene polymerization)

50 ml of dry oxygen-free toluene was sucked into a dry, O₂-free,magnetically stirred V4A steel autoclave which had been thoroughlyheated in vacuo. The D/A-metallocene catalyst (compound 10) waspreformed in toluene at room temperature with MAO (methylaluminoxane,10% strength in toluene, molecular weight 900 g/mol) in an atom(mol)ratio of Al/Zr=66,666: 1 in 15 minutes. An aliquot which contained1.5×10⁻⁷ mol of Zr and 1.0×10⁻² mol of Al in 6.8 ml was injected intothe autoclave with strict exclusion of air and the autoclave wassubsequently flushed with a further 50 ml of toluene. Polymerization wasthen carried out under a constant ethylene pressure of 10 bar at roomtemperature for 1 hour, the internal temperature rising to 42° C. Afterthe autoclave had been let down, the reaction mixture was introducedinto 500 ml of ethanol and 50 ml of concentrated aqueous hydrochloricacid and stirred overnight, and the polymer was filtered off, washedthoroughly with ethanol and dried to constant weight at 100° C. in acirculating air drying cabinet. The PE yield was 2.9 g, whichcorresponds to a catalyst activity of 19.3 tonnes of polymer per mole ofZr and hour. The limiting viscosity, measured in o-dichlorobenzene at140° C., was 4.36 dl/g. The DSC measurement gave a melting point of 139°C. and a heat of fusion of 164 J/g.

Examples 48 to 51

(Ethylene polymerization)

In other ethylene polymerization experiments, the procedure was as inExample 47, but the D/A-metallocene 7 was used as the catalyst anddifferent amounts of MAO were employed. The amount of Ti was 1×10⁻⁶ moland the autoclave was heated to about 100° C. The Al/Zr ratio was variedbetween 1250, 2500, 5000 and 10,000. In all 4 experiments, the catalystactivity was about 3 to 4 t of PE per mole of Ti and hour.

Example 52

(Ethylene polymerization)

The procedure was in accordance with Example 47, but 100 ml of toluenewas initially introduced directly into the autoclave. The autoclave washeated to 80° C., the catalyst was injected and the ethylene pressurewas adjusted to 10 bar. 1×10⁻⁶ mol of the compound 18 in 2.4 ml oftoluene, which had been preformed with 5×10⁻³ mol of MAO in 3.3 mol oftoluene, was used as the catalyst. The internal temperature rose from80° C. to 94° C. After 30 minutes, the polymerization was interrupted.The PE yield was 3.5 g, which corresponds to a catalyst activity ofabout 7 tonnes of polymer per mole of catalyst and hour. The limitingviscosity η was measured in ortho-dichlorobenzene at 140° C.; it was2.95 dl/g. The DSC measurement gave a melting point of 139° C. and aheat of fusion of 165 J/g.

Examples 53 to 56

(Ethylene polymerization)

The procedure was as in Example 51. The amount of Ti (compound 7) was1×10⁻⁶ mol and the Al/Zr ratio was 10,000. The autoclave was heated todifferent temperatures and the polymer properties of limiting viscosityand melting point T_(m) were measured.

T: RT to 60° = 7.2 dl/g T_(m) = 143° C. T: RT to 80° = 4.6 dl/g T_(m) =142° C. T: RT to 100° C. = 3.2 dl/g T_(m) = 144° C. T: RT to 120° = 2.2dl/g T_(m) = 140° C. (RT - Room temperature)

Example 57

(Ethylene polymerization)

The procedure was in accordance with Example 52, but the internaltemperature was adjusted to 100° C. 5×10⁻⁷ mol of the compound 24 in 0.4mol of chlorobenzene, which had been preformed with 5×10⁻³ mol of MAO in3.3 mol of toluene, were employed as the catalyst. The internaltemperature rose from 100° C. to 120° C. After polymerization for 30minutes, 6.2 g of PE had formed, which corresponds to a catalystactivity of about 25 tonnes of polymer per mole of catalyst and hour.The limiting viscosity η, measured in ortho-dichlorobenzene at 140° C.,was 1.85 dl/g.

Example 58

(Ethylene polymerization)

The procedure was in accordance with Example 57, but the compound 21 wasemployed as catalyst. In this case, the internal temperature rose from100° to 128° C. The PE yield was 7.9 g after 30 minutes, correspondingto a catalyst activity of about 31.6 tonnes per mole of catalyst andhour. The limiting viscosity η in ortho-dichlorobenzene at 140° C. was1.01 dl/g.

Example 59

(Ethylene polymerization)

The procedure was in accordance with Example 52, but the polymerizationwas started at 20° C. Metallocene 32 was used here as the catalyst. Forthis, 2.5×10⁻⁷ mol of catalyst were preformed with 2.5×10⁻³ mol of MAOin toluene. The internal temperature rose from 20° C. to 34° C. Afterpolymerization for 30 minutes, 1.3 g of PE had formed, which correspondsto a catalyst activity of 10.4 tonnes of polymer per mole of catalystand hour. The limiting viscosity η (ortho-dichlorobenzene, 140° C.) was5.3 dl/g.

The DSC measurement gave a melting point of 153° C. in the 1st heatingup at a rate of 20 K/minute. After quenching of the sample at 320K/minute, the melting maximum was determined at 146° C. in the 2ndheating up.

Example 60

(Ethylene polymerization)

The experiment was carried out in accordance with Example 47, but theD/A-metallocene employed as the catalyst was the compound meso-15. Theamount of Zr was 5×10⁻⁷ mol and the amount of Al was 1×10⁻² mol. Afteraddition of the catalyst and ethylene, the autoclave was heated rapidlyto about 1200° C. After a polymerization time of 30 minutes, 4.3 g ofpolyethylene was isolated, which corresponds to an activity of about 17t of PE per mole of Zr and hour. The limiting viscosity 71, measured at140° C. in o-dichlorobenzene, was 1.9 dl/g.

Example 61

(Diphenylphosphino-dichloroboranyl-bridged bis(indenyl)-zirconiumdichloride, compound 50)

0.011 mol of trimethylsilyl-dichloroboranyl-indene were added to asuspension of 0.012 mol of diphenylphosphino-indenyl-zirconiumtrichloride in 150 ml of toluene at room temperature. The reactionmixture was then stirred at 75° C. for 1 hour. After cooling andfiltration, 150 ml of hexane were added to the clear orange-coloredsolution, after which a heavy red oil and a pale yellow precipitate wereformed; the precipitate was filtered off, washed with hexane and driedin vacuo. The pale yellow solid was identified as the pure meso compoundby ¹H-NMR spectroscopy. The filtrate with the red oil was concentratedto 30 ml and added dropwise to 200 ml of hexane, after which a secondpale yellow precipitate formed, which was filtered off and dried invacuo. This product was identified as the pure rac isomer with the aidof X-ray structure analysis. Crystals suitable for the purpose werecultured by slow diffusion of hexane into a saturated CH₂Cl₂ solution atthe ambient temperature. The donor-acceptor bond P→B has a length of2.02 Å. The yield was 40% and the meso/rac ratio was 1:1. If thereaction mixture was stirred for 5 hours (instead of 1 hour), at 75° C.,an increased amount of the desired rac isomer was obtained; the meso/racratio was 1:4. At the same time, the overall yield rose slightly from40% to 45%.

Elemental analysis: 56.05% C (theoretical 55.90%), 4.35% H (4.38%)

Spectrum meso isomer: ¹H-NMR (400 MHz, CD₂Cl₂, room temperature RT):8.01 ppm (1H, d, 8.8 Hz); 7.8-7.0 ppm (several overlapping multiplets,28H); 6.94 ppm (1H, t, 3.3 Hz); 6.77 ppm (1H, d, 3.44 Hz); 6.31 ppm (1H,d, 8.7 Hz), ³¹P-NMR (161.9 MHz, CD₂Cl₂): 5.6 ppm. ¹¹B-NMR (80.2 MHz,CD₂Cl₂): −17.0 ppm (72 Hz).

Spectrum rac isomer: ¹H-NMR (400 MHz, CD₂Cl₂, RT): 8.39 ppm (1H, d, 8.5Hz); 7.68-7.05 ppm (27H, various overlapping multiplets); 6.65 ppm (1H,d, 2.9 Hz), 6.59 ppm (1H, t, 3.5 Hz); 6.51 ppm (1H, t, 2.8 Hz); 6.40 ppm(1H, d, 3.5 Hz) ³¹ P-NMR (161.9 MHz, CD₂Cl₂): 8.1 ppm ¹¹B-NMR (80.2 MHz,CD₂Cl₂)=−14.0 ppm (J_(P-B) 74 Hz).

Examples 62-64

(Dialkylphosphino-dichloroboranyl-bridged bis(indenyl)-zirconiumdichloride; alkyl=i-propyl=compound 51; ethyl=compound 52;methyl=compound 53)

0.016 mol of trimethylsilyl-dichloroboranyl-indene in 50 ml of toluenewas added to a suspension of 0.0157 mol ofdialkylphosphinoindenyl-zirconium trichloride in 250 ml of toluene atroom temperature. The reaction mixture was then heated for a few hourswhile stirring. After cooling and filtration, 300 ml of hexane wereadded to the clear orange-colored solution, after which a heavy red oiland a clear yellow solution were formed. Separation of the meso and racisomers was achieved by fractional crystallization from toluene/hexanesolutions.

Characterization of the compounds (NMR spectra in CD₂Cl₂ at RT; ¹H-NMR:400 MHz, ³¹P-NMR: 61.9 MHz, ¹¹B-NMR: 80.2 MHz):

rac compound 51 (i-Pr):

¹H-NMR: 8.41 ppm (1 H, d, 9.0 Hz); 8.31 ppm (1 H, d, 8.4 Hz); 7.84 ppm(1 H, d, 8.5 Hz); 7.64-7.24 ppm (6 H, various overlapping multiplets);6.70 ppm (2 H, m); 6.60 ppm (1 H, m): 3.78 ppm (1 H, m, P(CH(CH₃)₂)₂;3.21 ppm (1 H, m P(CH(CH₃)₂)₂); 1.81 ppm (6 H, m, P(CH(CH ₃)₂)₂; 1.72ppm (3 H, dd, P(CH(CH ₃)₂)₂, 14.9 Hz, 7.3 Hz); 1.32 ppm (3 H, dd,P(CH(CH ₃)₂)₂, 14.1 Hz, 7.4 Hz). ³¹P-NMR: 22.7 ppm. ¹¹B-NMR: −14.1 ppm(100 Hz).

Elemental analysis: 49.4% C (theoretical 48.9%), 4.6% H (4.4%).

meso compound 52 (Et):

¹H-NMR: 7.83 ppm (1 H, d, 9.0 Hz); 7.76 ppm (1 H, m); 7.63 ppm (1 H, d,7.2 Hz); 7.47 ppm (1 H, d, 8.5 Hz); 7.33 ppm (2 H, m); 7.20-7.03 ppm (4H, various overlapping multiplets); 6.76 ppm (2 H, m); 2.68 ppm (2 H, m,P(CH ₂CH₃)₂; 2.44 ppm (2 H, m P(CH ₂CH₃)₂); 1.62 ppm (3 H, m P(CH₂(CH₃)₂; 1.27 ppm (3 H, m, P(CH₂CH ₃)₂). ³¹P-NMR: 7.1 ppm. ¹¹B-NMR: −15.8ppm (100 Hz).

rac compound 52 (Et):

¹H-NMR: 8.28 ppm (1H, d, 8.6 Hz); 8.10 ppm (1 H, d, 8.6 Hz); 7.62 ppm (1H, d, 8.4 Hz); 7.46 ppm (1H, d, 8.5 Hz); 7.41-7.10 ppm (4 H, variousoverlapping multiplets); 6.81 ppm (1 H, m); 6.47 ppm (2 H, m): 6.38 ppm(1 H, d, 3.4 Hz), 2.68 ppm (2 H, m P(CH ₂CH₃)₂); 2.35 ppm (2 H, m, P(CH₂CH₃)₂); 1.30 ppm (6 H, m, P(CH₂CH ₃)₂). ³¹P-NMR: 12.3 ppm. ¹¹B-NMR:−15.7 ppm.

Elemental analysis: 47.6% C (theoretical 47.1%), 4.3% H (4.0%).

meso compound 53 (Me):

¹¹H-NMR: 7.84 ppm (1 H, d); 7.75 ppm (1 H, d, 8.2 Hz); 7.68 ppm (1 H, d,7.7 Hz); 7.51 ppm (1H, d, 8.5 Hz); 7.40-7.10 ppm (4 H, variousoverlapping multiplets); 6.77 ppm (2 H, br); 2.13 ppm (3 H, P(CH ₃)₂, d,11.8 Hz); 1.92 ppm (3 H, P(CH ₃)₂, d, 11.8 Hz). ³¹P-NMR: −8.4 ppm.¹¹B-NMR: −16.1 ppm (103 Hz).

rac compound 53 (Me):

¹H-NMR: 8.21 ppm (1 H, d, 8.7 Hz); 8.15 ppm (1 H, d, 8.6 Hz); 7.63 ppm(1 H, d, 8.5 Hz); 7.44-7.07 ppm (6 H, various overlapping multiplets);6.40 ppm (3 H, br); 2.03 ppm (3 H, d, P(CH ₃)₂, 11.9 Hz); 1.98 ppm (3 H,d, P(CH ₃)₂, 11.6 Hz). ³¹P-NMR: −1.5 ppm. ¹¹B-NMR: −16.0 ppm (119 Hz).

Example 65

(1,3-Bis(trimethylsilyl)-2-methylindene, compound 54)

500 ml of hexane and 70 ml of butyllithium (as a 2.5 molar solution inhexane) were introduced into a 1000 ml flask. 0.175 mol of2-methylindene was added dropwise at the ambient temperature; themixture was stirred for a further 10 hours. 0.18 mol of trimethylsilylchloride was then added dropwise at room temperature; the mixture wasstirred for a further 10 hours. LiCl was filtered off and 70 ml ofbutyllithium (as a 2.5 molar solution in hexane) were added to the clearfiltrate. After further stirring for 10 hours, 0.18 mol oftrimethylsilyl chloride was again added and the mixture was stirred fora further 10 hours. LiCl was filtered off and the solvent was removed invacuo. Compound 54 remained as a colorless oil. Yield: 85% of thetheoretical yield.

¹H-NMR (CD₂Cl₂): 7.51 ppm (1 H, d, 7.7 Hz); 7.38 ppm (1 H, d, 7.5 Hz);7.19 ppm (1 H, t, 7.4 Hz); 7.08 ppm (1 H, t, 7.3 Hz); 3.54 ppm (1H, s);2.32 ppm (3 H, s); 0.41 ppm (9 H, s, Si(CH ₃)₃); 0.0 ppm (9 H, s, Si(CH₃)₃).

Example 66

(Trimethylsilyl-dichloroboranyl-2-methylindene, compound 55)

0.096 mol of the compound 54 was introduced into a 250 ml flask equippedwith a dry ice condenser (−30° C.). 0.096 mol of BCl₃ was then added andthe mixture was stirred at the ambient temperature for 3 hours and at55° C. for 6 hours. The by-product (CH₃)₃SiCl was removed; a brown oilremained as the crude product. Distillation from cold trap to cold trapgave the compound 55 in a yield of 75% as a tacky solid.

¹H-NMR (CD₂Cl₂): 8.09 ppm (1 H, d, 7.9 Hz); 7.37 ppm (1 H, d, 7.6 Hz);7.26 ppm (1 H, t, 7.5 Hz); 7.16 ppm (1 H, t, 7.5 Hz); 3.89 ppm (1H, s);2.61 ppm (3 H, s); 0.0 ppm (9 H, s, Si(CH ₃)₃. ¹¹B-NMR (CD₂Cl₂): 31.9ppm.

Example 67

(Tributylstannyl-diethylphosphino-2-methylindene, compound 56)

The procedure was analogous to Example 7.

Example 68

(Diethylphosphino-2-methylindene-zirconium trichloride, compound 57)

The procedure was analogous to Example 8, but instead of toluene, CH₂Cl₂was used as the solvent. The reaction temperature was 25° C. Thepurification was carried out by Soxhlet extraction with CH₂Cl₂. Compound57 was obtained as an insoluble yellow solid in 78% of the theoreticalyield.

Example 69

((C₂H₅)₂P-BCl₂-bridged bis(2-methylindenyl)-zirconium chloride, compound58)

0.019 mol of compound 55 in 50 ml of toluene was added to a suspensionof 0.019 mol of compound 57 in 350 ml of toluene at room temperature.

The reaction mixture was then heated to 80° C. and stirred for 24 hours.After cooling and filtration, 300 ml of hexane were added to the clear,orange-colored solution, after which a heavy orange-colored oil and aclear yellow solution were formed. Concentration and cooling to −25° C.gave the compound rac-58 as a pale yellow powder.

¹H-NMR: 8.14 ppm (1 H, d, 8.6 Hz); 7.96 ppm (1 H, d, 8.9 Hz); 7.47-7.05ppm (6 H, various overlapping multiplets) 6.53 ppm (1H, d, 1.9 Hz); 6.47ppm (1 H, s); 3.0-2.55 ppm (4 H, various overlapping multiplets, P(CH₂CH₃)₂); 2.21 ppm (3 H, s, CH ₃); 2.08 ppm (3 H, s, CH ₃); 1.44 ppm (3H, m, P(CH₂CH ₃)₂), 1.07 ppm (3 H, m, P(CH₂(CH ₃)₂). ³¹P-NMR: 21.4 ppm.¹¹B-NMR: −14.7 ppm.

Example 70

(Propene polymerization)

A thoroughly heated 300 ml V4A steel autoclave was charged with 100 mlof dry, oxygen-free toluene and 0.5 ml of a 1 molartriisobutylaluminum/toluene solution. About 1 mol of propene was thentransferred into the autoclave. 1 ml of a chlorobenzene solution whichcomprised 4×10⁻⁶ mol of dimethylaniliniumtetrakis(pentafluorophenyl)borate was added in a pressure sluice to 3.1ml of a catalyst solution in toluene, which had been preformed at roomtemperature for 30 minutes and comprised 1×10⁻⁶ mol ofrac[(2-Me-ind)Et₂PBCl₂(2-Me-ind)ZrCl₂] and 0.1 mmol oftriisobutylaluminum (TiBA), and the mixture was topped up to 5 ml withtoluene. After the catalyst solution had been transferred into theautoclave under pressure, the internal temperature rose from 20° C. to48° C. in spite of external cooling with dry ice/acetone.

20 minutes after addition of the catalyst, the polymerization wasinterrupted and the contents of the autoclave were extracted by stirringin 500 ml of ethanol and 50 ml of concentrated aqueous hydrochloric acidfor 2 hours. The white polypropylene powder was then isolated byfiltration, washed with ethanol and dried at 115° C.

Polymer yield: 11.6 g

Catalyst activity: 34.8 tonnes of i-PP per mole of catalyst and hour TheDSC measurement gave, in the 2nd heating up, a melting point T_(m)32155° C. The NMR measurement gave an isotactility index I.I.=88%

The limiting viscosity [η] measured in ortho-dichlorobenzene (ODCB) at140° C. was 3.60 dl/g, corresponding to a molecular weight M_(visc)=798kg/mol (calculated by the method of Atkinson et al., Makromol. Chem.(1976), 177, 213).

With rac-52 under comparable experimental conditions at a polymerizationtemperature of between 10° and 20°, an i-PP was obtained with I.I.=92%and [η]=1.20 dl/g, corresponding to a calculated average molecularweight M_(visc)=169 kg/mol.

Example 71

(Ethylene polymerization)

A thoroughly heated 300 ml V4A steel autoclave was charged with 100 mlof dry, oxygen-free toluene and heated up to 100° C. A constant 10 barwas established with ethylene and the catalyst was added by means of apressure sluice.

5×10⁻⁷ mol of meso-[(ind)Et₂PBCl₂(ind)ZrCl₂] which had been preformedwith 5×10⁻³ mol of MAO in 5 ml of toluene at RT for 15 minutes, wereused as the catalyst.

The internal temperature rose to 111° C. during the polymerization.

Polyethylene yield after 30 minutes: 12.1 g

Catalyst activity: 48.4 tonnes of polymer per mole of catalyst and hour

Limiting viscosity in ortho-dichlorobenzene at 140° C.: [η]=0.91 dl/gDSC analysis: T_(m)=136° C.

Example 72

The procedure was as in Example 70, but with the difference that it wascarried out under a propene pressure of only 2 bar. The internaltemperature rose from 20° C. to 23° C. The melting point of thepolypropylene formed in this case was T_(m)=158° C.

What is claimed is:
 1. A process for the preparation of a high-meltingpolyolefin by homo- or copolymerization of one or more monomers from thegroup consisting of α-olefins having 2 or more C atoms in the presenceof an organometallic catalyst which can be activated by a cocatalyst,which comprises employing as the organometallic catalyst a metallocenecompound or π complex compound of the formula

in which CpI and CpII are two identical or different carbanions having acyclopentadienyl-containing structure, in which one to all the H atomscan be substituted by identical or different radicals from the groupconsisting of linear or branch C₁-C₂₀-alkyl, which can bemonosubstituted to completely substituted by halogen, mono- totrisubstituted by phenyl or mono- to trisubstituted by vinyl,C₆-C₁₂-aryl, halogenoaryl having 6 to 12 C atoms, organometallicsubstituents, including silyl, trimethylsilyl or ferrocenyl, or one ortwo can be replaced by D and A, D denotes a donor atom, which canadditionally carry substituents and has at least one free electron pairin its bond state, A denotes an acceptor atom, which can additionallycarry substituents and has an empty orbital capable of accepting a pairof electrons in its bond state, wherein D and A are linked by areversible coordinate bond such that the donor group assumes a positivecharge and the acceptor group assumes a negative charge, M represents atransition metal of sub-group III, IV, V or VI of the Periodic Table ofthe Elements, including the lanthanides and actinides, X denotes oneanion equivalent and n denotes the number zero, one, two, three or four,depending on the charge of M, or a π complex compound, or metallocenecompound of the formula

 in which πI and πII represent different charged or electrically neutralπ systems which can be fused with one or two unsaturated or saturatedfive- or six-membered rings, D denotes a donor atom, which is asubstituent of πI or part of the π system of πI and has at least onefree electron pair in its bond state, A denotes an acceptor atom, whichis a substituents of πII or part of the π system of πII and has an emptyorbital capable of accepting a pair of electrons in its bond state,wherein D and A are linked by a reversible coordinate bond such that thedonor group assumes a positive charge and the acceptor group assumes anegative charge, and where at least one of D and A is part of theassociated π system, wherein D and A in their turn can carrysubstituents, wherein each π system and each fused-on ring system cancontain one or more D or A or D and A and wherein πI and πII in thenon-fused or in the fused form, one to all the H atoms of the π systemindependently of one another can be substituted by identical ordifferent radicals from the group consisting of linear or branchedC₁-C₂₀-alkyl, which can be monosubstituted to completely substituted byhalogen, mono- to trisubstituted by phenyl or mono- to trisubstituted byvinyl, C₆-C₁₂-aryl, halogenoaryl having 6 to 12 C atoms, organometallicsubstituents, including silyl, trimethylsilyl or ferrocenyl, or one ortwo can be replaced by D and A, so that the reversible coordinate D→Abond (i) is formed between D and A which are both parts of the π systemor the fused-on ring system, or (ii) of which D or A is part of the πsystem and in each case the other is substituent of the non-fused πsystem or the fused-on ring system, or (iii) both D and A are suchsubstituents, and in the case of (iii) at least one additional D or A orboth is (are) parts of the π system or the fused-on ring system, M and Xhave the above meanings and n denotes the number zero, one, two, threeor four, depending on the charges of M and those of π-I and π-II.
 2. Theprocess as claimed in claim 1, wherein the metallocene compound or the πcomplex compound is employed as the catalyst in an amount of 10¹ to 10¹²mol of monomers per mole of metallocene or π complex compound.
 3. Theprocess as claimed in claim 1, wherein the reaction is carried out inthe presence of solvents selected from the group consisting of aromatichydrocarbons, saturated hydrocarbon, aromatic halohydrocarbons andsaturated halohydrocarbons.
 4. The process as claimed in claim 1,wherein, in the metallocene compound or the π complex compound, thecarbanions CpI and CpII or the π system πI denote a cyclopentadienylskeleton from the group consisting of cyclopentadiene, substitutedcyclopentadiene, indene, substituted indene, fluorene and substitutedfluorene, in which 1 to 4 substituents from the group consisting ofC₁-C₂₀-alkyl, C₁-C₂₀-alkoxy, halogen, C₆-C₁₂-aryl, halogenophenyl, D andA, wherein D and A, are present per cyclopentadiene or fused-on benzenering, it being possible for fused-on aromatic rings to be partly orcompletely hydrogenated.
 5. The process as claimed in claim 1, wherein,in the metallocene compound, elements selected from the group consistingof N, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br and I, are present as donoratoms D.
 6. The process as claimed in claim 1, wherein, in themetallocene compound, elements selected from the group consisting of B,Al, Ga, In and Tl are present as acceptor atoms A.
 7. The process asclaimed in claim 1, wherein in the metallocene compound or π complexcompound, donor-acceptor bridges selected from the group consisting ofN→B, N→Al, P→B, P→Al, O→B, O→Al, Cl→B, Cl→Al, C═O→B, C═O→Al are present.8. The process as claimed in claim 1, wherein, in the metallocenecompound, M represents Sc, Y, La, Sm, Nd, Lu, Ti, Zr, Hf, Th, V, Nb, Taor Cr.
 9. The process as claimed in claim 1, wherein the metallocenecompound or π complex compound is employed as a catalyst system togetherwith an aluminoxane, a borane or borate and, optionally, furthercocatalysts and/or metal-alkyls.
 10. The process as claimed in claim 1,wherein a rearrangement product of said metallocene compound or πcomplex compound with self-activation, with which, after opening of theD/A bond, the acceptor atom A bonds an X ligand to form a zwitterionicmetallocene complex structure or π complex structure, where a positivecharge is generated in the transition metal M and a negative charge isgenerated in the acceptor atom A, and where a further X ligandrepresents H or substituted or unsubstituted C, in the bond of which tothe transition metal M the olefin insertion takes place for thepolymerization, preferably 2 X ligands being linked to a chelate ligand,is employed.
 11. The process as claimed in claim 1, wherein in said πcomplex compound D is part of the ring of the associated π system. 12.The process as claimed in claim 1, wherein a reaction product of theformulae (XI(a-d) of an ionizing agent with said metallocene compound orπ complex according to formula (I) or (XIII)

in which Anion represents the entire bulky, poorly coordinating anionand Base represents a Lewis base, is employed.
 13. The process asrecited in claim 1, directed to the preparation of a high-meltingpolyolefin selected form the group consisting of HDPE, LLDPE withbutylene, hexene or octene, iPP, and sPP.
 14. The process as claimed inclaim 1, wherein said process is directed to the preparation of a linearpolyethylene having a melting point of 140-160° C.
 15. The processaccording to claim 5, wherein, in the metallocene compound, elementsselected from the group consisting of N, P, O and S are present as donoratoms D.
 16. The process according to claim 6, wherein, in themetallocene compound, elements selected from the group consisting of B,Al, and Ga, are present as acceptor atoms A.
 17. The process accordingto claim 8, wherein, in the metallocene compound, M represents Ti, Zr,Hf, V, Nb or Ta.
 18. The process according to claim 14, wherein saidmelting point ranges from 142 to 160° C.
 19. The process according toclaim 18, wherein said melting point ranges from 144 to 160° C.
 20. Theprocess according to claim 19, wherein said melting point ranges from146 to 160° C.
 21. A linear polyethylene having a melting point of 140to 160° C., which is prepared by polymerization of ethylene in thepresence of an organometallic catalyst which can be activated by acocatalyst, which comprises employing as the organometallic catalyst ametallocene pound or π complex compound of the formula

in which CpI and CpII are two identical or different carbanions having acyclopentadienyl-containing structure, in which one to all the H atomscan be substituted by identical or different radicals from the groupconsisting of linear or branched C₁-C₂₀-alkyl, which can bemonosubstituted to completely substituted by halogen, mono- totrisubstituted by phenyl or mono- to trisubstituted by vinyl,C₆-C₁₂-aryl, halogenoaryl having 6 to 12 C atoms, organometallicsubstituents, including silyl, trimethylsilyl or ferrocenyl, or one ortwo can be replaced by D and A, D denotes a donor atom, which canadditionally carry substituents and has at least one free electron pairin its bond state, A denotes an acceptor atom, which can additionallycarry substituents and has an empty orbital capable of accepting a pairof electrons in its bond state, wherein D and A are linked by areversible coordinate bond such that the donor group assumes a positivecharge and the acceptor group assumes a negative charge, M represents atransition metal of sub-group III, IV, V or VI of the Periodic Table ofthe Elements, including the lanthanides and actinides, X denotes oneanion equivalent and N denotes the number zero, one, two, three or four,depending on the charge of M, or a π complex compound, or metallocenecompound of the formula

 in which πI and πII represent different charged or electrically neutralπ systems which can be fused with one or two unsaturated or saturatedfive- or six-membered rings, D denotes a donor atom, which is asubstituent of πI or part of the π system of πI and has at least onefree electron pair in its bond state, A denotes an acceptor atom, whichis a substituent of πII or part of the π system of πII and has an emptyorbital capable of accepting a pair of electrons in its bond state,wherein D and A are linked by a reversible coordinate bond such that thedonor group assumes a positive charge, and the acceptor group assumes anegative charge, and where at least one of D and A is part of theassociated π system, wherein D and A in their turn can carrysubstituents, wherein each π system and each fused-on ring system cancontain one or more D or A or D and A and wherein πI and πII in thenon-fused or in the fused form, one to all the H atoms of the π systemindependently of one another can be substituted by identical ordifferent radicals from the group consisting of linear or branchedC₁-C₂₀-alkyl, which can be monosubstituted to completely substituted byhalogen, mono- to trisubstituted by phenyl or mono- to trisubstituted byvinyl, C₆-C₁₂-aryl, halogenoaryl having 6 to 12 C atoms, organometallicsubstituents, including silyl, trimethylsilyl or ferrocenyl, or one ortwo can be replaced by D and A, so that the reversible coordinate D→Abond (i) is formed between D and A which are both parts of the π systemor the fused-on ring system, or (ii) of which D or A is part of the πsystem and in each case the other is substituent of the non-fused πsystem or the fused-on ring system, or (iii) both D and A are suchsubstituents, and in the case of (iii) at least one additional D or A orboth is (are) parts of the π system or the fused-on ring system, M and Xhave the above meanings and n denotes the number zero, one, two, threeor four depending on the charges of M and those of π-I and π-II.
 22. Thepolyethylene according to claim 21, wherein said melting point rangesfrom 142 to 160° C.
 23. The polyethylene according to claim 22, whereinsaid melting point ranges from 144 to 160° C.
 24. The polyethyleneaccording to claim 23, wherein said melting point ranges from 146 to160° C.